CN1220304A - Refrigerating machine oil composition - Google Patents
Refrigerating machine oil composition Download PDFInfo
- Publication number
- CN1220304A CN1220304A CN 97122040 CN97122040A CN1220304A CN 1220304 A CN1220304 A CN 1220304A CN 97122040 CN97122040 CN 97122040 CN 97122040 A CN97122040 A CN 97122040A CN 1220304 A CN1220304 A CN 1220304A
- Authority
- CN
- China
- Prior art keywords
- oil
- refrigerator oil
- composition
- refrigerator
- viscosity
- 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.)
- Granted
Links
Landscapes
- Lubricants (AREA)
Abstract
The present invention relates to a refrigerator oil composition. It contains paraffin slack wax cracked C5-C18 mixed alpha olefine polymer oil with viscosity of 10-15 sq.mm/s, also can include epoxide type stabilizing agent, organic phosphate type lubricant and phenol type antioxidant, etc.. Said invented refrigerator oil possesses good consolute with fluorochlorohydrogenhydrocarbon, at the same time, also possesses high viscosity index, higher flashing point, lower floc point and good thermochemical stability, specially is suitable for refrigerator oil using fluorochlorohydrogenhydrocarbon as refrigerating agent, also can be used as refrigerator oil using fluorochlorohydrocarbon, propane isobutane or ammonia as refrigerating agent.
Description
The invention belongs to lubricating oil composition, exactly is a kind of refrigerated machine oil composition.
The steam compression type refrigeration device generally is made up of compressor, condenser, expansion valve and vaporizer, its action principle is the heat that absorbs surrounding medium when utilizing the refrigeration agent gasification, and temperature is reduced, and by compressor refrigeration agent is restored then to be liquid, again gasification so moves in circles again.In this refrigerator, being separated of refrigeration agent and oil generally should do not taken place.If refrigeration agent and lubricating oil are separated in compressor, running gear will be nibbled or other problem because of insufficient lubrication causes card, reduces the life-span of equipment greatly; If be separated in vaporizer, the lubricating oil that sticks on the vaporizer will influence heat transfer efficiency, causes the decline of refrigerating efficiency, sometimes even can stop up kapillary or expansion valve and cause accident.Therefore good refrigerator oil must have good mutual solubility with refrigeration agent, and the two is not separated under use temperature.
Good refrigerator oil must have viscosity temperature characteristic preferably.The use temperature of lubricating oil in refrigeration compression system is very wide, in the cylinder of some compressor, sometimes can contact 150 ℃ high temperature, in vapo(u)rization system, then may contact one 40 ℃ low temperature, therefore it is little to require oil viscosity to vary with temperature, to guarantee that lubricating oil all has good lubricity and startability under differing temps.
The refrigerator oil of excellent property also should have higher flash-point, flash-point is low, volatility is high oil easily in the volatilization of high-temperature exhaust air valve place, become sticky and the generation that generates carbon distribution, carbide can cause the safety failure of compressor.
Fluorine chlorine hydrogen hydrocarbon is a compression-type refrigerator refrigeration agent commonly used, comprise monochlorodifluoromethane (HCFC-22), Dichloromonofluoromethane (HCFC-21), 1-chloro-1,2,2,2 Tetrafluoroethanes (HCFC-124), 1-chloro-1,1,2,2-Tetrafluoroethane (HCFC-125a), 1-chloro-1, the azeotropic mixtures (R502) of 1-C2H4F2 C2H4F2 (HCFC-142b) and monochlorodifluoromethane (HCFC-22) and a chloropentafluoroethane (HCFC-115) etc. wherein especially with the excellent performance of HCFC-22, use extensively, its consumption accounts for 90% of whole fluorine chlorine hydrogen hydrocarbon, is widely used as the refrigeration agent of domestic air conditioner and freezer.But HCFC-22 polarity is stronger, makes the mutual solubility difference of hydro carbons lubricating oil of itself and different structure very big.
The stronger alkylbenzene of polarity with HCFC-22 good mutual solubility is arranged, but its viscosity temperature characteristic and lubricity are poor, and flash-point is low, and price is higher, and be difficult to produce high-viscosity products, therefore adopt alkylbenzene and the fusion of cycloalkyl Dormant oils to make the refrigerator oil of HCFC-22 at present mostly.
The naphthene base crude oil of deep refining has been owing to removed the component that many and HCFC-22 have good mutual solubility, so the mutual solubility of itself and HCFC-22 is relatively poor, is unsuitable for doing the refrigerator oil of HCFC-22.
Shallow degree purified naphthene base crude oil has mutual solubility preferably with HCFC at normal temperatures, but its viscosity temperature characteristic is poor, and flash-point is low, and the stability when contacting with refrigeration agent is also relatively poor.
The monoolefine stand oil has good viscosity temperature characteristic and low temperature flowability, higher flash-point, have good solubility and thermo-chemical stability with CFC12, so it can be as being the lubricating oil of refrigeration agent with the fluorochlorohydrocarbon, but being unsuitable for as the lubricating oil of making refrigeration agent with chlorine fluorine hydrogen hydrocarbon.The synthetic hydrocarbon oil that Fr.2099664 has proposed with the oligomeric one-tenth of monoolefine is the method for raw material allotment refrigerator oil, and this synthetic hydrocarbon oil is by consisting of C
nH
2n(n=26～30) monoolefine is polymerized, and it has lower condensation point and flock point, is applicable to that work is the refrigerator oil of refrigeration agent with Chlorofluorocarbons (CFCs) (CFC12), is the refrigerator oil of refrigeration agent but be unsuitable for fluorine chlorine hydrogen hydrocarbon.Fr.2299398 has proposed with C
10The polyolefin oil of the oligomeric one-tenth of alhpa olefin is through the method for the saturated synthetic hydrocarbon oil allotment refrigerator oil that obtains of hydrogenation.This oil has good low-temperature performance, very high viscosity index and the mutual solubility good with fluorochlorohydrocarbon, but should oil and chlorine fluorine hydrogen hydrocarbon do not dissolve each other, therefore being unsuitable for allocating with fluorine chlorine hydrogen hydrocarbon is the refrigerator oil of refrigeration agent.
The objective of the invention is to based on prior art, particularly have a good mutual solubility and the refrigerated machine oil composition that have higher viscosity index, higher flash-point and good low-temperature performance of fluorine chlorine hydrogen hydrocarbon coolant of a kind of and refrigeration agent is provided.
It is 10～150mm that refrigerated machine oil composition provided by the invention contains viscosity
2/ s, 30～100mm preferably
2The soft wax cracked C of/s
5～C
18The mixed stand oil, described soft wax oleaginousness is generally 15～40%.In addition, in order to improve the stability of oil product, refrigerator oil provided by the invention also can be the hydrogenation saturated oil of above-mentioned alpha-olefin polymerization oil.
Refrigerator oil provided by the invention is according to conventional alpha-olefin polymerization technology synthetic, adds catalyzer in raw material olefin, reacts 2～3 hours down at 125～135 ℃, after the cooling-sedimentation branch removes sediment, adds the Ca (OH) of 2～3% (wt) in product
2, 2～3% (wt) carclazyte, in 70～80 ℃ of following neutralization reactions 30～90 minutes, remove by filter carclazyte, underpressure distillation under about 1.33KPa, cutting viscosity is 10～150mm
2The fraction of/s is refrigerator oil provided by the invention.Catalyst for polymerization is general cationic Lewis acid of this technology or Lewis acid solvay-type catalyzer, as AlCl
3, BF
3.ROH, AlCl
3.NaCl, AlCl
3.Eto, AlCl
3.ROH, AlCl
3.R
2C=0 etc.Catalyst levels be olefin feedstock weight 2～2.5% (with Al
2Cl
3Meter).
If obtain the hydrogenation saturated oil, can after removing carclazyte, carry out hydrofining, and then carry out underpressure distillation.Be generally secondary hydrogenation, one-stage hydrogenation carries out under 275 ℃, 5MPa, and catalyzer is Ni-W-Mo-F, and secondary hydrogenation carries out under 265 ℃, 5MPa, and catalyzer is Pt-α-Al
2O
3, the one-stage hydrogenation catalyzer needs through prevulcanized, and the secondary hydrogenation catalyzer needs to handle through hydrogen reducing.
In addition, in refrigerator oil provided by the invention, add additive,, can further improve its performance as stablizer, lubricant, oxidation inhibitor etc.
Described stablizer is the general epoxy compounds class stablizer in this area, can be glycidyl ether, epoxy grease, epoxy aliphatic ester, ether epoxy, epoxy phosphorus benzene bis-acid potassium ester etc., and consumption is 0.1～5% of a composition weight, preferably 0.2～1.0%.
Described lubricant is the general phosphoric acid ester lubricant in this area, as trimethylphenyl phosphoric acid ester, triphenyl, octyl group diphenyl phosphoester, benzyl diphenyl phosphoester, phenyl thiophosphatephosphorothioate etc., its consumption is 0.1～5% of a composition weight, preferably 0.2～2%.
Described oxidation inhibitor is the general phenol type antioxidant in this area, as 2,6 ditertiary butyl p cresol, 2-tertiary butyl 4-cresols, 2,6-di-tert-butylphenol, 4,4 '-tetramethyl-two (2, the 6-di-tert-butylphenol), Resorcinol, 2-Naphthol etc., its consumption is 0.1～3% of a composition weight.
Refrigerated machine oil composition provided by the invention can also comprise kilfoam, and as dimethyl silicone oil, its consumption is generally 0.001～0.005% of composition weight.
Refrigerated machine oil composition provided by the invention can also comprise sanitas, and as benzotriazole, its consumption is generally 0.01～0.1% of composition weight.
Above raw material and reagent all can be the commercial goods.
Refrigerator oil provided by the invention has following advantage:
1. have good mutual solubility with fluorine chlorine hydrogen hydrocarbon, can reach-22 ℃ as Kraft point with HCFC-22;
2. has higher viscosity index, generally than 30～50 ℃ of commercially available refrigerator innages;
3. has higher flash-point, generally than 10～30 ℃ of commercially available refrigerator innages;
4. has extremely low flock point, generally than low 15～25 ℃ of commercially available refrigerator oil;
5. have good thermochemical stability,, then can further improve stability if it is saturated to carry out hydrogenation;
6. has very low sulphur nitrogen impurity content.
Refrigerator oil provided by the invention can be used as the lubricating oil of making refrigeration agent with fluorochlorohydrocarbon, is especially suitable for use as to being the domestic air conditioning cold compressor oil of refrigeration agent with fluorine chlorine hydrogen hydrocarbon.In addition, because refrigerator oil provided by the invention has excellent low-temperature fluidity and oilness, therefore also can be used for propane Trimethylmethane and ammonia is in the refrigerating apparatus of refrigeration agent.
The invention will be further described below by embodiment.
Raw materials used alkene is Fushun oil one factory among the embodiment provides.
Embodiment 1
With soft wax (oleaginousness 20%) cracked C
5～C
18Mixed be raw material, add 2% anhydrous AlCl
3, reacted 2 hours down at 130 ℃, after the cooling-sedimentation branch goes sediment but, in product, add 2% Ca (OH)
2, 3% carclazyte is in 70～80 ℃ of following neutralization reactions 50 minutes, removes by filter carclazyte, under reduced pressure cut the cut of ISO VG56 and make base oil.Therefrom take out 100g oil, add epoxy soybean oil 0.3g, 2,6 ditertbutylparacresol 0.2g, trimethylphenyl phosphoric acid ester 1.5g is deployed into refrigerator oil, and its physicochemical property sees Table 1.
Embodiment 2
With soft wax (oleaginousness 35%) cracked C
5～C
18Mixed be raw material, carry out catalyzed polymerization and aftertreatment by the condition of embodiment 1, then cut the cut of ISO VG56, take out 100g oil, add phenyl glycidyl ether 0.5g, 2,6-di-tert-butylphenol 0.4g, triphenyl 2g is deployed into refrigerator oil, and its physicochemical property sees Table 1.
Embodiment 3
With soft wax (oleaginousness 20%) cracked C
5～C
12Mixed be raw material, use AlCl
3Make catalyzer, press the method polymerization and the aftertreatment of example 1, again after hydrogenation is saturated, the cut of cutting ISO VG56 is made base oil, therefrom takes out 100g, adds neopentyl glycol two cyclic glycerol ether 1.0g, octyl phenyl phosphoric acid ester 2.0g, 2-tertiary butyl 4-cresols 0.5g is deployed into refrigerator oil, and its physicochemical property sees Table 1.
Embodiment 4
With soft wax (oleaginousness 30%) cracked C
5～C
10Mixed be raw material, press example 1 condition polymerization and aftertreatment, after hydrogenation was saturated, the cut that cuts ISO VG56 was made base oil, gets 100g, add Epoxy oil carboxylic butyl ester 0.5g, phenyl thiophosphatephosphorothioate 1.0g, 2,6 ditertbutylparacresol 0.3g, be deployed into refrigerator oil, its physicochemical property sees Table 1.
Embodiment 5
With soft wax (oleaginousness 30%) cracked C
5～C
10Mixed be raw material, use AlCl
3.NaCl make catalyzer, press example 1 condition polymerization and aftertreatment, after hydrogenation was saturated, the cut that cuts ISO VG32 was made base oil, get 100g, add 2 ethyl hexanoic acid glycidyl ester 0.2g, trioctylphosphine phosphoesterase 30 .5g, Resorcinol 0.2g, benzotriazole 0.02g, silicone oil 0.001g is deployed into refrigerator oil, and its physicochemical property sees Table 1.
Comparative Examples 1
To commonly used in the market be that the refrigerator oil (trade(brand)name suniso4GS sun oil Co. production) of refrigeration agent carries out same physico-chemical property evaluation with HCFC-22, the results are shown in Table 1.
Comparative Examples 2
To commonly used in the market be that the another kind of refrigerator oil (trade(brand)name suniso 4GS SD1, sun oil Co. produces) of refrigeration agent carries out same physico-chemical property evaluation with HCFC-22, the results are shown in Table 1.Table 1
| Kinematic viscosity mm 2/s | Viscosity index | Pour point ℃ | Flash-point ℃ | Density g/cm 3(20℃) | Acid number mgKOH/g | Flock point ℃ | Kraft point ℃ | The Philips test (250 ℃, 90h) | ||
| ?40℃ | ?100℃ | |||||||||
| Embodiment 1 | ?54.31 | ?7.16 | ?87 | ?-42 | ?212 | ?0.8730 | ?0.02 | -52 | ????5 | By |
| Embodiment 2 | ?52.65 | ?6.48 | ?59 | ?-44 | ?217 | ?0.8752 | ?0.01 | -60 | ????-10 | By |
| Embodiment 3 | ?54.04 | ?6.97 | ?80 | ?-42 | ?214 | ?0.8723 | ?0.02 | -52 | ????3.5 | By |
| Embodiment 4 | ?53.58 | ?6.58 | ?61 | ?-43 | ?220 | ?0.8745 | ?0.01 | -57 | ????-2 | By |
| Embodiment 5 | ?31.22 | ?4.81 | ?56 | ?-48 | ?191 | ?0.8698 | ?0.01 | -60 | ????-22 | By |
| Comparative Examples 1 | ?54.18 | ?6.14 | ?30 | ?-35 | ?182 | ?0.9158 | ?0.02 | -38 | ????6 | Do not pass through |
| Comparative Examples 2 | ?54.47 | ?6.14 | ?29 | ?-35 | ?185 | ?0.9167 | ?0.03 | -43 | ????4.5 | By |
| Experimental technique | ?????GB/T265 | ?GB/T ?2541 | ?GB/T ?3535 | ?GB/T ?3536 | ?GB/T ?1884 | ?GB/T ?4945 | ?GB/T 12577 | JISK2211 appendix 3 * | ????GB/T ????12577 | |
*: the method by JISK2211 appendix 3 is carried out.In the test tube of internal diameter 10mm and high 10cm, add the 1ml sample and weigh, slowly add HCFC-22 in the test tube then, the weight ratio for the treatment of oil and HCFC-22 is 1.5: 8.5 o'clock, stops to add and sealing, and measures the solvent temperature that oil and HCFC-22 are separated then.
As can be seen from Table 1, refrigerator oil provided by the invention and HCFC-22 have good mutual solubility, also have higher viscosity index, higher flash-point simultaneously.Therefore extremely low flock point and good thermochemical stability are especially suitable for use as with fluorine chlorine hydrogen hydrocarbon and are the refrigerator oil of refrigeration agent, are applicable to that also with fluorochlorohydrocarbon, propane Trimethylmethane or ammonia be the refrigerator oil of refrigeration agent.
Claims (7)
1. refrigerated machine oil composition, it is characterized in that containing viscosity is 10～150mm
2The soft wax cracked C of/s
5～C
18The mixed stand oil.
2. according to the described composition of claim 1, it is characterized in that viscosity is 30～100mm
2/ s.
3. according to claim 1 or 2 described compositions, it is characterized in that described stand oil is saturated through hydrogenation.
4. according to the described composition of claim 1, it is characterized in that it can also comprise: with the composition weight benchmark, 0.1～5% epoxy compounds class stablizer, 0.1～5% phosphoric acid ester lubricant, 0.1～3% phenol type antioxidant.
5. according to the described composition of claim 4, it is characterized in that epoxy compounds class stablizer is selected from one of glycidyl ether, epoxidised fats, epoxyfatty acid fat, ether epoxy, epoxy phosphorus benzene bis-acid potassium ester.
6. according to the described composition of claim 4, it is characterized in that described phosphoric acid ester lubricant is selected from one of trimethylphenyl phosphoric acid ester, triphenyl, octyl group diphenyl phosphoester, benzyl diphenyl phosphoester, phenyl thiophosphatephosphorothioate.
7. according to the described refrigerator oil of claim 4, it is characterized in that phenol type antioxidant is selected from 2,6 ditertiary butyl p cresol, 2-tertiary butyl 4-cresols, 2,6-di-tert-butylphenol, 4, one of 4 '-tetramethyl-two (2, the 6-di-tert-butylphenol), Pyrogentisinic Acid, β-Nai phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122040A CN1054154C (en) | 1997-12-16 | 1997-12-16 | Refrigerating machine oil composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122040A CN1054154C (en) | 1997-12-16 | 1997-12-16 | Refrigerating machine oil composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1220304A true CN1220304A (en) | 1999-06-23 |
| CN1054154C CN1054154C (en) | 2000-07-05 |
Family
ID=5176635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122040A Expired - Lifetime CN1054154C (en) | 1997-12-16 | 1997-12-16 | Refrigerating machine oil composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1054154C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070503B (en) * | 2006-05-08 | 2010-12-01 | 北京福润联石化科技开发有限公司 | Refrigerated machine oil composition |
| CN101397522B (en) * | 2007-09-28 | 2012-02-15 | 中国石油化工股份有限公司 | Environment-friendly type refrigerating machine oil composition |
| CN102977862A (en) * | 2012-12-21 | 2013-03-20 | 中国人民解放军空军油料研究所 | Cooling liquid composition |
| CN108138073A (en) * | 2015-09-25 | 2018-06-08 | 爱德龙润滑油公司 | Lubricant compositions |
| CN112266814A (en) * | 2020-11-11 | 2021-01-26 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigerating machine oil, working fluid composition for compressor, and compressor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177643B (en) * | 2007-09-29 | 2012-09-05 | 北京福润联石化科技开发有限公司 | Refrigerating machine oil combination and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882380A (en) * | 1987-07-07 | 1989-11-21 | Union Carbide Chemicals And Plastics Company Inc. | Process for the production of impact polypropylene copolymers |
| GB2272000B (en) * | 1992-10-30 | 1997-03-26 | Castrol Ltd | A method of inhibiting corrosion |
| US5667349A (en) * | 1995-04-26 | 1997-09-16 | Cincinnati Milacron Inc. | Method of making pull tabs and lubricant therefor |
-
1997
- 1997-12-16 CN CN97122040A patent/CN1054154C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070503B (en) * | 2006-05-08 | 2010-12-01 | 北京福润联石化科技开发有限公司 | Refrigerated machine oil composition |
| CN101397522B (en) * | 2007-09-28 | 2012-02-15 | 中国石油化工股份有限公司 | Environment-friendly type refrigerating machine oil composition |
| CN102977862A (en) * | 2012-12-21 | 2013-03-20 | 中国人民解放军空军油料研究所 | Cooling liquid composition |
| CN102977862B (en) * | 2012-12-21 | 2015-04-08 | 中国人民解放军空军油料研究所 | Cooling liquid composition |
| CN108138073A (en) * | 2015-09-25 | 2018-06-08 | 爱德龙润滑油公司 | Lubricant compositions |
| CN112266814A (en) * | 2020-11-11 | 2021-01-26 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigerating machine oil, working fluid composition for compressor, and compressor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054154C (en) | 2000-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4431557A (en) | Refrigerator oil composition(s) | |
| EP0498152B1 (en) | Lubricant composition for fluorinated refrigerants | |
| CN1044292A (en) | Be used for polyoxyethylene glycol lubricant of refrigerator and preparation method thereof | |
| US6516837B2 (en) | Method of introducing refrigerants into refrigeration systems | |
| AU730693B2 (en) | Lubricating oil composition for refrigerators and method for lubrication with the composition | |
| AU683517B2 (en) | Lubricating oil for compression refrigerator | |
| JPH0559388A (en) | Refrigerating machine oil composition | |
| US5154846A (en) | Fluorinated butylene oxide based refrigerant lubricants | |
| JPH06102792B2 (en) | Lubricating oil for fluorine-containing alkane refrigerant | |
| JP2595346B2 (en) | Refrigeration oil composition for car air conditioners | |
| CN1054154C (en) | Refrigerating machine oil composition | |
| CN1869178A (en) | Refrigeration lubricant composition | |
| US4983313A (en) | Refrigerating machine oil composition | |
| US5705086A (en) | Refrigeration oils comprising esters of hindered alcohols | |
| US5454966A (en) | Stabilized chlorine-containing refrigeration compositions | |
| JP3319499B2 (en) | Lubricating oil composition for refrigerator and lubricating method using the composition | |
| JP2930963B2 (en) | Lubricating oil composition for CFC refrigerant | |
| CN1217738A (en) | Lubricating oil for compression refrigerators, working fluid for refrigerators and method for lubricating refrigeration system | |
| JP2008069366A (en) | Lubricating oil composition for refrigerator and lubricating method using the composition | |
| GB1594189A (en) | Working fluid for refrigeration or heat pump apparatus | |
| CN114381325B (en) | Refrigerator oil composition and application thereof | |
| JP3545143B2 (en) | Lubricating oil composition for refrigerator and lubricating method using the composition | |
| JP2928413B2 (en) | Lubricant | |
| JP4209601B2 (en) | Refrigeration equipment | |
| IL92617A (en) | Liquid compositions containing an ethyl or methyl hydrofluorocarbon and a carboxylic acid ester lubricant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20000705 |