CN1473916A - Method for improving miscibility of refrigerating machine oil and refrigerant and refrigerating machine oil prepared by said method - Google Patents
Method for improving miscibility of refrigerating machine oil and refrigerant and refrigerating machine oil prepared by said method Download PDFInfo
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- CN1473916A CN1473916A CNA031367267A CN03136726A CN1473916A CN 1473916 A CN1473916 A CN 1473916A CN A031367267 A CNA031367267 A CN A031367267A CN 03136726 A CN03136726 A CN 03136726A CN 1473916 A CN1473916 A CN 1473916A
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Abstract
The method of improving the miscibility between the refrigerating machine oil and refrigerant hydrofluorocarbons (HFCs) is to add to mineral-base refrigerating machine oil certain amount of nano particles with specific surface-modified matrix to make the mineral-base refrigerating machine oil possess proper miscibility with refrigerant HFCs while raising the antifriction performance of the iron-base or aluminum-base part surface. The added nano particles are ones containing Ti, Mo, Ni, Zr or La element and of size 1-150 nm. The added nano particles, the mineral-base refrigerating machine oil and HFCs constitute one system with excellent lubricant performance, electrically insulating performance and stability.
Description
Technical field
Invention relates to a kind of refrigerator oil that improves the method for intermiscibility between refrigerator oil and the refrigeration agent and utilize this method preparation.Relate in particular to a kind of refrigerator oil that improves the method for intermiscibility between mineral substance refrigerator oil and hydrogen fluorohydrocarbon (HFCs) the class refrigeration agent and utilize this method preparation.According to method provided by the invention, can make mineral substance refrigerator oil and HFCs refrigeration agent have the intermiscibility of appropriateness, thereby being used as, mineral refrigeration oil adopts the lubricating oil of HFCs class material as refrigeration, heat pump or the device of working medium.
Background technology
At present, in many artificial refrigerating fields of need using such as family expenses refrigeration, commercial refrigeration, industrially drying, chemical engineering and environment manual shift, HFCs class material generally CFC alternative s be used as the working medium of refrigeration system.In the alternative engineering of HCFCs working medium, HFCs also is main candidate substances.
Consistency between common mineral substance lubricating oil and the HFCs class material and poorly soluble can not be directly used in the refrigeration system that adopts HFCs working medium.The main at present lubricating oil that uses lipid refrigerator oil (being called for short POE) as the refrigeration system that adopts HFCs working medium.
POE class refrigerator oil, oilness is relatively poor, water-absorbent and water-disintegrable strong.Adopt the system or the device of lipid refrigerator oil, need carefully to select fluids such as smear metal oil that employed raw and auxiliary material, the course of processing use and scavenging solution, otherwise can cause the obstruction of expansion gear because chemical reaction etc. produce cured, flocculent substance.At present, adopt the refrigeration system of HFCs/POE system to have many problems to need further to solve at aspects such as efficiency, working reliabilities.
Adding additive in POE is to adopt more being used to improve the method for the lubricity of POE/HFCs system at present.Add T.C.P or phosphoric acid lipid additive, can obtain being equivalent to the lubricity of CFCs/ mineral oil.Owing to do not change the character of POE class refrigerator oil, thereby can't solve the problem that the refrigeration system that adopts the HFCs/POE system exists, as the consistency of material, floss precipitation, expansion gear obstruction etc. as strong strong solvent at all.
The invention provides a kind of method of improving mineral refrigeration oil and HFCs refrigeration agent intermiscibility.According to method provided by the invention, can make mineral substance refrigerator oil and HFCs refrigeration agent have the intermiscibility of appropriateness, thereby being used as, mineral refrigeration oil adopts the lubricating oil of HFCs class material as refrigeration, heat pump or the device of working medium.
The invention provides the mineral refrigeration oil that can have appropriate intermiscibility with the HFCs refrigeration agent.The present invention discusses for the refrigerator system of the reciprocation compressor that adopts the HFC134a refrigeration agent, but also contains refrigeration, heating or the device of the mixture of HFCs refrigeration agent as all compressors of refrigeration agent applicable to other HFCs refrigeration agent of any employing or employing.
Summary of the invention
For fear of problems such as the consistency that adopts POE class refrigerator oil to face as refrigeration, heat pump or the device of working medium, floss precipitation, expansion gear obstructions, the invention provides intermiscibility and deliquescent method between a kind of HFCs of improvement class refrigeration agent and the mineral substance refrigerator oil such as material as lubricating oil, HFCs class material.By method provided by the invention, can make the mineral substance refrigerator oil as the lubricating oil that adopts HFCs class material as refrigeration, heat pump or the device of working medium, reduce working medium displacement cost.
The invention provides intermiscibility and deliquescent method between a kind of HFCs of improvement class refrigeration agent and the mineral substance refrigerator oil, it is characterized in that adding the certain amount of nano particle to mineral refrigeration oil.
The invention provides intermiscibility and deliquescent mineral refrigeration oil between a kind of HFCs of improvement class refrigeration agent and the mineral substance refrigerator oil.This mineral refrigeration oil contains nanoparticle, has appropriate mutual solvability with the HFCs refrigeration agent.
Embodiment
1. nanoparticle is carried out finishing.The certain amount of nano particle is joined in the toluene solution of the hard fatty acid ester that contains 1%-10%, use the ultra-sonic oscillation device, under the condition of heating, vibrated 2-6 hour, the centrifugation nanoparticle, under-10 ℃ to 50 ℃ temperature, vacuum-drying;
2. in mineral refrigeration oil, add through behind the nanoparticle of finishing, use the ultra-sonic oscillation device to add and get final product after thermal oscillation fully disperses it.
According to method provided by the invention, common mineral substance refrigerator oil after adding nanoparticle, has the consistency of appropriateness and the solvability of appropriateness to the HFCs refrigeration agent, the compressor that can reflux well of the lubricating oil in refrigeration system or the device.
Common mineral substance refrigerator by in, add contain Ti with or Mo and or Ni and or La and or the nanoparticle of Zr element.The nanoparticle that is added is a metallics; The size of nanoparticle at 1nm between the 150nm; Add the ratio of weight of nanoparticle and lubricating oil between 0.1 ‰ to 45.6 ‰.Through after the finishing, nanoparticle has good dispersiveness, stability and electrical insulation capability in mineral oil.
In addition, also can add contain Ti with or Mo and or Ni and or La and or the nanoparticle of Zr element.The nanoparticle that is added is a metal oxide particle; The size of nanoparticle at 1nm between the 150nm; Add the ratio of weight of nanoparticle and lubricating oil between 0.1 ‰ to 45.6 ‰.Through after the finishing, nanoparticle has good dispersiveness, stability and electrical insulation capability in mineral oil.
In addition, also can add contain Ti with or Mo and or Ni and or La and or the nanoparticle of Zr element.The nanoparticle that is added is a phosphate particle; The size of nanoparticle at 1nm between the 150nm; Add the ratio of weight of nanoparticle and lubricating oil between 0.1 ‰ to 45.6 ‰.Through after the finishing, nanoparticle has good dispersiveness, stability and electrical insulation capability in mineral oil.
In addition, also can add contain Ti with or Mo and or Ni and or La and or the nanoparticle of Zr element.The nanoparticle that is added is a nitrate particle; The size of nanoparticle at 1nm between the 150nm; Add the ratio of weight of nanoparticle and lubricating oil between 0.1 ‰ to 45.6 ‰.
In addition, also can add contain Ti with or Mo and or Ni and or La and or the nanoparticle of Zr element.The nanoparticle that is added is the hydrochloride particle; The size of nanoparticle at 1nm between the 150nm; Add the ratio of weight of nanoparticle and lubricating oil between 0.1 ‰ to 45.6 ‰.
Can prepare the mineral refrigeration oil that can have appropriate intermiscibility according to aforesaid method with the HFCs refrigeration agent.Contain 0.1 ‰ to 45.6 ‰ nanoparticle in this refrigerator oil, used mineral refrigeration oil is the mixture of alkyl benzene refrigerator oil or paraffin class refrigerator oil or alkyl benzene refrigerator oil and paraffin class refrigerator oil, the particle of contained nanoparticle is that size arrives the sphere of 150nm or the particle of other shape at 1nm, and contained nanoparticle is by containing titanium elements or making with nickel element or with zr element or with molybdenum element or with the substrate material of lanthanum element.
Inventive embodiment is discussed for the refrigerator system of the reciprocation compressor that adopts the HFC134a refrigeration agent, but also contains refrigeration, heating or the device of the mixture of HFCs refrigeration agent as all compressors of refrigeration agent applicable to other HFCs refrigeration agent of any employing or employing.
In nominal viscosity is No. 22 common mineral refrigeration oil, after adding 0.1 ‰ to 15.6 ‰ TiO2 (a) nanoparticle, oil concentration less than 20% condition under, in-32 ℃ to 65 ℃ temperature range, do not have tangible demixing phenomenon with the mixed system of HFC134a refrigeration agent, show that intermiscibility is good.
In nominal viscosity is No. 22 common mineral refrigeration oil, add 0.1 ‰ to 15.6 ‰ TiO2 (a) nanoparticle, after using the ultra-sonic oscillation device to add thermal oscillation it is fully disperseed, typical experimental data is as follows:
| Experimental project | Experimental technique | The experiment test result |
| Density, 15 ℃ of g/cm 3 | ????ASTM?D?1250 | ????0.906 |
| 40 ℃ of kinematic viscosity, mm 2/s | ????ASTM?D?445 | ????23.6 |
| 100 ℃ of kinematic viscosity, mm 2/s | ????ASTM?D?445 | ????4.15 |
| Flash-point COC ℃ | ????ASTM?D?92 | ????175 |
| Pour point ℃ | ????ASTM?D?97 | ????-43 |
| Resistivity cm | ????ANSI/86 | ????56×10 12 |
In nominal viscosity is No. 22 common mineral refrigeration oil, make new refrigerator oil after adding 0.1 ‰ to 15.6 ‰ TiO2 (a) nanoparticle, the working volume that adopts this refrigerator oil is 5.56cm
3The link-type compressor and working volume to be 2.96cm3 slip pipe formula compressor as follows by the salient features test data of experiment before and after the accelerated aging experiment in 500 hours:
| Experimental project | Working volume is 5.56cm 3The link-type compressor | Working volume is 2.96cm 3Slip pipe formula compressor | ||
| Before the experiment | After the experiment | Before the experiment | After the experiment | |
| Refrigerating duty W | ????142.6 | ????142.2 | ????80.3 | ????80.5 |
| Power input W | ????135.7 | ????134.6 | ????88.5 | ????87.9 |
| Noise dB (A) | ????38.7 | ????37.4 | ????36.2 | ????35.8 |
| Remarks | Connecting rod material is an aluminium alloy; Crankshaft material is a carbon steel; Piston and cylinder material are cast iron | Slip pipe, piston and crankshaft material are carbon steel; The cylinder material is a cast iron | ||
In nominal viscosity is No. 22 common mineral refrigeration oil, make new refrigerator oil after adding 0.1 ‰ to 15.6 ‰ TiO2 (a) nanoparticle, this refrigerator oil is used for the household refrigerator-freezer that useful volume is 245 liters, and through 5000 hours normal utilization and operations, the oil return result was as follows:
1. nominal viscosity is No. 22 common mineral refrigeration oil, CFC12 refrigeration agent, oil return ratio: 93.2%;
2. the refrigerator oil in the embodiment of the invention, HFC134a refrigeration agent, oil return ratio: 92.0%;
3. nominal viscosity is No. 22 POE oil (VG 22 ester), the HFC134a refrigeration agent, oil return ratio: 87.0%. adopts method provided by the invention, can fundamentally change the dependence to POE lubricating oil of refrigeration, heat pump or the device of employing HFCs working medium, reduces working medium displacement cost.
Claims (18)
1. method of improving refrigerator oil and refrigeration agent consistency, refrigeration agent wherein is fluoroether refrigerant (HFCs), and the refrigerator oil that this refrigeration agent adopts is a mineral refrigeration oil, and the feature of this method is that (1) carries out finishing to nanoparticle; (2) add the certain amount of nano particle to mineral refrigeration oil.
2. method according to claim 1, one of step is, nanoparticle is joined in the toluene solution of the hard fatty acid ester that contains 1%-10%, use the ultra-sonic oscillation device, under the condition of heating, vibrated the centrifugation nanoparticle 2-6 hour, under-10 ℃ to 50 ℃ temperature, vacuum-drying.
3. method according to claim 1, two of step are that adding is used the ultra-sonic oscillation device to add thermal oscillation it is fully disperseed through behind the nanoparticle of finishing in mineral refrigeration oil.
4. method according to claim 1, wherein, the size of the nanoparticle that is added at 1nm between the 150nm.
5. method according to claim 1, the ratio of the nanoparticle that is added and the weight of the mineral refrigeration oil that will join wherein is in the scope between 0.1 ‰ fluoroether refrigerants to 45.6 ‰.
6. according to the described method of claim 1, wherein the nanoparticle that is added is the metallics of the metallics of the metallics of the metallics of the metallics of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the mixture that contains titanium, molybdenum, zirconium, lanthanum particle.
7. according to the described method of claim 1, wherein the nanoparticle that is added is the metal oxide particle of the metal oxide particle of the metal oxide particle of the metal oxide particle of the metal oxide particle of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the mixture that contains the metal oxide particle of titanium, molybdenum, zirconium, lanthanum element.
8. method according to claim 1, wherein the nanoparticle that is added is the nitrate particle of the nitrate particle of the nitrate particle of the nitrate particle of the nitrate particle of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the mixture that contains the nitrate of titanium, molybdenum, zirconium, lanthanum element.
9. according to the described method of claim 1, wherein the nanoparticle that is added is the phosphate particle of the phosphate particle of the nitrate particle of the phosphate particle of the phosphate particle of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the phosphatic mixture that contains titanium, molybdenum, zirconium, lanthanum element.
10. method according to claim 1, wherein the nanoparticle that is added is the hydrochloride particle of the hydrochloride particle of the hydrochloride particle of the hydrochloride particle of the hydrochloride particle of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the mixture that contains the hydrochloride of titanium, molybdenum, zirconium, lanthanum element.
11. method according to claim 1, wherein the nanoparticle that is added is the sulphate particles of the sulphate particles of the sulphate particles of the sulphate particles of the sulphate particles of titanium elements or molybdenum element or nickel element or zr element or lanthanum element or the mixture that contains the vitriol of titanium, molybdenum, zirconium, lanthanum element.
12. a mineral refrigeration oil comprises alkyl phenyl mineral oil and paraffin base mineral oil, it is characterized in that containing in this mineral refrigeration oil the mutual deliquescent nanoparticle that makes it to have with fluoroether refrigerant (HFCs) appropriateness.
13. mineral refrigeration oil according to claim 12, wherein the size of contained nanoparticle at 1nm between the 150nm.
14. mineral refrigeration oil according to claim 12, the ratio of wherein contained nanoparticle and the weight of the mineral refrigeration oil that will join is in the scope between 0.1 ‰ to 45.6 ‰.
15. mineral refrigeration oil according to claim 12, wherein contained nanoparticle is the nanoparticle that contains titanium elements.
16. mineral refrigeration oil according to claim 12, wherein contained nanoparticle is the nanoparticle that contains nickel element.
17. mineral refrigeration oil according to claim 12, wherein contained nanoparticle is the nanoparticle that contains zr element.
18. mineral refrigeration oil according to claim 12, wherein contained nanoparticle is the nanoparticle that contains lanthanum element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03136726 CN1226401C (en) | 2003-05-21 | 2003-05-21 | Method for improving miscibility of refrigerating machine oil and refrigerant and refrigerating machine oil prepared by said method |
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| CN 03136726 CN1226401C (en) | 2003-05-21 | 2003-05-21 | Method for improving miscibility of refrigerating machine oil and refrigerant and refrigerating machine oil prepared by said method |
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| CN1473916A true CN1473916A (en) | 2004-02-11 |
| CN1226401C CN1226401C (en) | 2005-11-09 |
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| CN 03136726 Expired - Fee Related CN1226401C (en) | 2003-05-21 | 2003-05-21 | Method for improving miscibility of refrigerating machine oil and refrigerant and refrigerating machine oil prepared by said method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143975B (en) * | 2007-04-29 | 2010-11-17 | 北京建筑工程学院 | Modified preparation method for nano nickel ferrite micro-particle capable of dispensing in alkyl benzene refrigerator oil, alkyl benzene refrigerator oil thereof and preparation method for the alkyl |
| CN102679603A (en) * | 2011-03-15 | 2012-09-19 | 河南新飞电器有限公司 | Energy-saving refrigerator |
| CN104403637A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Tetrafluoropropene composition with good lubricant compatibility and preparation method thereof |
| CN104403638A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Preparation method for nanoparticle enhanced refrigerant |
| CN104403639A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Preparation method for enhanced heat transfer type nano-refrigerant |
| CN104479632A (en) * | 2014-11-14 | 2015-04-01 | 巨化集团技术中心 | Preparation method of nano refrigerant with good lubricant compatibility |
| CN106047447A (en) * | 2016-05-27 | 2016-10-26 | 武汉杰生润滑科技有限公司 | Method for improving intermiscibility of refrigerant lubricant and refrigerant and preparation of refrigerant lubricant |
-
2003
- 2003-05-21 CN CN 03136726 patent/CN1226401C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143975B (en) * | 2007-04-29 | 2010-11-17 | 北京建筑工程学院 | Modified preparation method for nano nickel ferrite micro-particle capable of dispensing in alkyl benzene refrigerator oil, alkyl benzene refrigerator oil thereof and preparation method for the alkyl |
| CN102679603A (en) * | 2011-03-15 | 2012-09-19 | 河南新飞电器有限公司 | Energy-saving refrigerator |
| CN104403637A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Tetrafluoropropene composition with good lubricant compatibility and preparation method thereof |
| CN104403638A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Preparation method for nanoparticle enhanced refrigerant |
| CN104403639A (en) * | 2014-11-14 | 2015-03-11 | 巨化集团技术中心 | Preparation method for enhanced heat transfer type nano-refrigerant |
| CN104479632A (en) * | 2014-11-14 | 2015-04-01 | 巨化集团技术中心 | Preparation method of nano refrigerant with good lubricant compatibility |
| CN104403638B (en) * | 2014-11-14 | 2017-05-10 | 巨化集团技术中心 | Preparation method for nanoparticle enhanced refrigerant |
| CN104403639B (en) * | 2014-11-14 | 2017-05-10 | 巨化集团技术中心 | Preparation method for enhanced heat transfer type nano-refrigerant |
| CN104479632B (en) * | 2014-11-14 | 2017-08-15 | 巨化集团技术中心 | A kind of preparation method of the nano refrigerant with good lubrication agent compatibility |
| CN104403637B (en) * | 2014-11-14 | 2017-10-03 | 巨化集团技术中心 | A kind of preparation method of the tetrafluoropropene composition with good lubrication agent compatibility |
| CN106047447A (en) * | 2016-05-27 | 2016-10-26 | 武汉杰生润滑科技有限公司 | Method for improving intermiscibility of refrigerant lubricant and refrigerant and preparation of refrigerant lubricant |
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| Publication number | Publication date |
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| CN1226401C (en) | 2005-11-09 |
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Granted publication date: 20051109 Termination date: 20140521 |