CN1279139C - Substitute refrigerant for freon-12 centrifugal cold water machine set - Google Patents
Substitute refrigerant for freon-12 centrifugal cold water machine set Download PDFInfo
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- CN1279139C CN1279139C CN 01120436 CN01120436A CN1279139C CN 1279139 C CN1279139 C CN 1279139C CN 01120436 CN01120436 CN 01120436 CN 01120436 A CN01120436 A CN 01120436A CN 1279139 C CN1279139 C CN 1279139C
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Abstract
The present invention relates to a refrigerant for a centrifugal water chilling machine set, particularly to a substitute refrigerant for a freon-12 centrifugal water chilling machine set. The refrigerant contains monochloro difluoro methane, 1, 1, 1, 2, 3, 3, 3-heptafluoropropane and 1-monochloro-1, 1-difluoroethane and isobutane can be optionally added to form a quaternary mixture. The refrigerant is prepared by physically mixing the ingredients in a liquid phase state according to corresponding proportions. The refrigerant has the advantages of environmental protection, high safety and reliability, equivalent refrigerating efficiency to that of CFC-12, no need for changing the compressor and the main parts of the system and reforming the production line and direct filling, has slightly better performance than that of freon-12, and can be used as a substitute refrigerant for the existing freon-12 centrifugal water chilling machine set.
Description
Technical field
The invention belongs to a kind of refrigeration agent, relate in particular to the refrigeration agent that a kind of centrifugal refrigerating machines is used.
Background technology
Since F-12 (CFC-12) have hypotoxicity, not flammable, do not have a corrosion, with other material characteristics such as compatibility mutually, be widely used in refrigeration system and some other fields for a long time.But after finding that from 1974 CFC class material has serious destruction to atmospheric ozone layer, caused increasingly extensive in the world attention, and decision progressively limits production and the use of CFCs.China will stop using CFC-12 on January 1st, 2010.At present, as the refrigeration agent of centrifugal refrigerating machines, the use of CFC-12 also accounts for quite great proportion.
Parameters such as the wheel speed of CFC-12 radial compressor and impeller basic size are to determine according to character such as the hot rerum natura of certain vaporization temperature, condensing temperature and refrigeration agent CFC-12, molar masss.In general, the CFC-12 centrifugal refrigerating machines can only use CFC-12 as refrigeration agent, if use other refrigeration agent instead, because surrogate and the difference of CFC-12 aspect rerum naturas such as hot rerum natura and molar mass, not only can not reach the efficient of former centrifugal water chillers, even may works better.Use other some surrogates instead, during as HFC-134a, all need compressor impeller is retrofited or changed some parts.So, select the alternative refrigerant of CFC-12 centrifugal refrigerating machines, more much more difficult than piston-type, screw-type water chiller, not only requiring has close hot rerum natura with CFC-12, also has particular requirement.
At present, the main refrigeration agent of CFC-12 has HFC-134a as an alternative, and its advantage is not damage the ozone layer, thermal property and CFC-12 are very close, but because the molar mass of HFC-134a is 102.03, and the molar mass of CFC-12 is 120.91, because the difference between their molar masss, when directly charging, tip speed must be more about 15% than the raising of CFC-12, so impeller and transmitting gear must be changed, the pipe of interchanger need be reset, and expense will increase greatly.Otherwise surge will take place in compressor when oepration at full load, can't works better.In addition, some mixture replacing things of CFC alternative-12 have also been developed both at home and abroad, R401 series, R406A, THR01 and THR02 or the like, these mix surrogates CFC alternative-12 o'clock in piston-type, screw-type water chiller, and operating performance is all fine, but when being used for centrifugal refrigerating machines, because the difference of molar mass, if the size and the size of not changing impeller, not only do not reach the refrigeration of crude CFC-12, also may make the handpiece Water Chilling Units can't works better.At present, still do not have both at home and abroad and a kind ofly can be directly used in the CFC-12 centrifugal refrigerating machines and need not to transform the alternative refrigerants of its equipment.
In patent PCT/US96/14882, quaternary mixture that the 600a of the HCFC-142b of HFC-227ea, 5%-25% of a kind of HCFC-22 with 21%-75%, 15%-60% and 1%-10% the forms surrogate as CFC-12 is disclosed.But description according to the front, centrifugal refrigerating machines has particular requirement to the thermal property and the molar mass of refrigeration agent, the surrogate molar mass must be approaching with the molar mass (120.91) of CFC-12, and inlet and outlet pressure is suitable with CFC-12, also need take all factors into consideration factors such as combustibility, refrigeration performance, be not that any proportioning of above-mentioned quaternary mixture all is applicable to centrifugal refrigerating machines.Such as, the various proportionings of in its patent working example, mentioning: " 4/15/40/41 R-600a/142b/227ea/22; 4/15/30/51 R-600a/142b/227ea/22; 8/13/38/41 R-600a/142b/227ea/22; 2/16/41/41 R-600a/142b/227ea/22; 4/20/45/31 R-600a/142b/227ea/22 and 4/8/32/56 R-600a/142b/227ea/22 ", their molar mass is respectively 107.8,101.6,103.7,110.0,112.2 and 101.6, all the molar mass (120.91) with CFC-12 differs bigger, can not directly charge at all and be used in existing centrifugal refrigerating machines.And for example, in the claim scope, choose 40% HCFC-22,40% HFC-227ea, 15% HCFC-142b and 5% HC-600a composition mixture, its molar mass is 107.16, than the molar mass of CFC-12 little 11.4%, directly filling to substitute uses; Choose 21% HCFC-22,55% HFC-227ea, 22% HCFC-142b and 2% HC-600a composition mixture, its molar mass is 122.0, and is suitable with the molar mass of CFC-12, but its volume refrigerating capacity compressor only is 90.5% of CFC-12.So the claim scope of this patent is inapplicable to centrifugal refrigerating machines.
Summary of the invention
The present invention is intended to develop a kind of new refrigerant that is used for centrifugal refrigerating machines, promptly be used for substituting the surrogate of existing CFC-12 centrifugal refrigerating machines, make its not only compliance with environmental protection requirements, safely, reliably, refrigerating efficiency is suitable with CFC-12, and need not change existing equipment and refrigeration oil, can directly charge.
The present invention is achieved through the following technical solutions:
A kind of alternative refrigerant of F-12 centrifugal refrigerating machines is characterized in that this refrigeration agent contains monochlorodifluoromethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1-one chloro-1, and three kinds of materials of 1-C2H4F2 C2H4F2, its each components contents (mass percent) is
Monochlorodifluoromethane: 28-30%
1,1,1,2,3,3,3-heptafluoro-propane: 60%-62%
1-one chloro-1,1-C2H4F2 C2H4F2: 10%-12%
Three kinds of component concentrations of above-mentioned refrigeration agent (mass percent) respectively are:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 67%-69%
1-one chloro-1,1-C2H4F2 C2H4F2: 15%-17%
Refrigeration agent of the present invention is characterized in that above-mentioned refrigeration agent also contains Trimethylmethane, and its component concentration (mass percent) is respectively:
Monochlorodifluoromethane: 27%-29%
1,1,1,2,3,3,3-heptafluoro-propane: 58%-60%
1-one chloro-1,1-C2H4F2 C2H4F2: 9%-11%
Trimethylmethane: 2%-4%
Four kinds of component concentrations (mass percent) of above-mentioned refrigeration agent can be respectively:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 66%-68%
1-one chloro-1,1-C2H4F2 C2H4F2: 14%-16%
Trimethylmethane: 2%-3%
Refrigeration agent provided by the invention, its preparation method are above-mentioned various components to be carried out physical mixed by its corresponding mixture ratio get final product under liquid phase state.
Monochlorodifluoromethane in the said components (HCFC-22), its molecular formula are CHClF
2, molar mass is 86.47, and normal boiling point is-40.81 ℃, and critical temperature is 96.15 ℃, and emergent pressure is 4.99MPa.
1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea), its molecular formula are CF
3CHFCF
3, molar mass is 170.03, and normal boiling point is-15.61 ℃, and critical temperature is 101.74 ℃, and emergent pressure is 2.929MPa.
Trimethylmethane (HC-600a), its molecular formula are CH (CH
3)
2CH
3, molar mass is 58.12, and normal boiling point is-11.61 ℃, and critical temperature is 134.7 ℃, and emergent pressure is 3.64MPa.
1-one chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), its molecular formula is CH
3CClF
2, molar mass is 100.49, and normal boiling point is-9.0 ℃, and critical temperature is 137.1 ℃, and emergent pressure is 4.12MPa.
The present invention has the following advantages and beneficial effect:
A. environmental performance
The destruction potential (ODP) of this refrigeration agent ozonosphere is very little, approaches zero, and its Greenhouse effect coefficient (GWP) is more much smaller than R12.This shows that the present invention meets the protection ozonosphere fully, reduce the environmental protection requirement of Greenhouse effect, table 2 has provided the environmental performance comparison with F-12.
Table 2 environmental performance relatively
Refrigeration agent | F-12 | The present invention |
ODP | 1.0 | 0.021 |
GWP (100 years) | 8500 | 2044 |
B. thermal parameter:
Under the standard design operating mode, the force value of vaporizer, condenser inner refrigerant, the pressure ratio and the F-12 of compressor are close, and exhaust temperature is also lower than F-12.
Table 3 thermal parameter relatively
Refrigeration agent | F-12 | The present invention |
Evaporating pressure (kPa) | 387.1 | 374.7 |
Condensing pressure (kPa) | 1345.5 | 1410.9 |
Pressure ratio | 3.48 | 3.77 |
Exhaust temperature (℃) | 89.2 | 78.9 |
C. thermal property
The thermal property of this refrigeration agent (COP, cold and volume refrigerating capacity compressor) is a little more than F-12, referring to table 4.This shows that this refrigeration agent can directly use the compressor of F-12 and need not change.
Table 4 thermal property relatively
Refrigeration agent | F-12 | The present invention |
COP | 1.0 | 1.01 |
Cold | 1.0 | 1.03 |
Volume refrigerating capacity compressor | 1.0 | 1.01 |
In sum, the present invention not only thermal property and F-12 is approaching, does not damage the ozone layer substantially, can reduce the Greenhouse effect influence, compliance with environmental protection requirements; And nontoxic, not flammable, can directly charge, the major parts in compressor and the system need not changed, and production line need not transformed; On performance, also slightly be better than F-12, can be used as the alternative refrigerant of existing centrifugal refrigerating machines F-12.
Embodiment
Refrigeration agent of the present invention, it is characterized in that by monochlorodifluoromethane (HCFC-22), 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227ea) and 1-one chloro-1, three kinds of materials of 1-C2H4F2 C2H4F2 (HCFC-142b) are formed, and also can add Trimethylmethane (HC-600a) again and form quaternary mixed refrigerant.But,,,, need the different mix refrigerants that charge proportioning as flooded type or dry type to dissimilar vaporizers in order to satisfy the particular requirement of radial compressor because the slip temperature of these two groups of mixtures is all bigger.
For the centrifugal water-cooled unit of dry type evaporator, the component concentration of tertiary mixture (mass percent) is:
Monochlorodifluoromethane: 28-30%
1,1,1,2,3,3,3-heptafluoro-propane: 60%-62%
1-one chloro-1,1-C2H4F2 C2H4F2: 10%-12%
For the centrifugal water-cooled unit of flooded type vaporizer, the component concentration of tertiary mixture (mass percent) is:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 67%-69%
1-one chloro-1,1-C2H4F2 C2H4F2: 15%-17%
For the centrifugal water-cooled unit of dry type evaporator, Trimethylmethane (HC-600a) can also be added, on aforementioned tertiary mixture basis to have better oil soluble.Its component concentration (mass percent) is:
Monochlorodifluoromethane: 27%-29%
1,1,1,2,3,3,3-heptafluoro-propane: 58%-60%
1-one chloro-1,1-C2H4F2 C2H4F2: 9%-11%
Trimethylmethane: 2%-4%
For the centrifugal water-cooled unit of flooded type vaporizer, also Trimethylmethane (HC-600a) can be added on aforementioned tertiary mixture basis, to have better oil soluble.Its component concentration (mass percent) is:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 66%-68%
1-one chloro-1,1-C2H4F2 C2H4F2: 14%-16%
Trimethylmethane: 2%-3%
In order to help understanding, enumerate several specific embodiments below to invention and advantage thereof.
Embodiment:
Embodiment 1: 28%HCFC-22,61%HFC-227ea and 11%HFC-142b are carried out physical mixed under liquid phase.
Embodiment 2: 15%HCFC-22,68%HFC-227ea and 17%HFC-142b are carried out physical mixed under liquid phase.
Embodiment 3: 28%HCFC-22,60%HFC-227ea, 3%HC-600a and 9%HFC-142b are carried out physical mixed under liquid phase.
Embodiment 4: 15%HCFC-22,67%HFC-227ea, 2.5%HC-600a and 15.5%HFC-142b are carried out physical mixed under liquid phase.
Under the standard design operating mode of centrifugal refrigerating machines, the thermal property of the foregoing description refrigeration agent is listed in the table 1.
Table 1 embodiment thermal property
Embodiment | Example 1 | Example 2 | Example 3 | Example 4 | CFC-12 |
Evaporating pressure kPa | 363.6 | 368.5 | 374.7 | 376.5 | 387.1 |
Condensing pressure kPa | 1384.1 | 1398.9 | 1410.9 | 1415.1 | 1345.5 |
Pressure ratio | 3.81 | 3.80 | 3.77 | 3.76 | 3.48 |
Exhaust temperature ℃ | 79.4 | 80.0 | 78.9 | 79.5 | 89.2 |
COP * | 1.01 | 1.02 | 1.01 | 1.01 | 1.0 |
Cold * | 1.02 | 1.03 | 1.03 | 1.04 | 1.0 |
Volume refrigerating capacity compressor * | 1.0 | 1.01 | 1.01 | 1.01 | 1.0 |
ODP | 0.023 | 0.021 | 0.021 | 0.019 | 1.0 |
GWP | 2176 | 2322 | 2044 | 2198 | 8500 |
Remarks:
*The corresponding ratio of expression and CFC-12.
Claims (3)
1. the alternative refrigerant of a F-12 centrifugal refrigerating machines, it is characterized in that: this refrigeration agent contains monochlorodifluoromethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1-one chloro-1, three kinds of materials of 1-C2H4F2 C2H4F2, its mass percentage content is respectively:
Monochlorodifluoromethane: 28%-30%
1,1,1,2,3,3,3-heptafluoro-propane: 60%-62%
1-one chloro-1,1-C2H4F2 C2H4F2: 10%-12%.
2. the alternative refrigerant of a F-12 centrifugal refrigerating machines, it is characterized in that: this refrigeration agent contains monochlorodifluoromethane, 1,1,1,2,3,3,3-heptafluoro-propane and 1-one chloro-1, three kinds of materials of 1-C2H4F2 C2H4F2, its mass percentage content is respectively:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 67%-69%
1-one chloro-1,1-C2H4F2 C2H4F2: 15%-17%.
3. the alternative refrigerant of a F-12 centrifugal refrigerating machines, it is characterized in that: this refrigeration agent contains monochlorodifluoromethane, 1,1,1,2,3,3,3-heptafluoro-propane, 1-one chloro-1, four kinds of materials of 1-C2H4F2 C2H4F2 and Trimethylmethane, its mass percentage content is respectively:
Monochlorodifluoromethane: 14%-16%
1,1,1,2,3,3,3-heptafluoro-propane: 67%-68%
1-one chloro-1,1-C2H4F2 C2H4F2: 14%-16%
Trimethylmethane: 2%-3%
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CN 01120436 CN1279139C (en) | 2001-07-13 | 2001-07-13 | Substitute refrigerant for freon-12 centrifugal cold water machine set |
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CN 01120436 CN1279139C (en) | 2001-07-13 | 2001-07-13 | Substitute refrigerant for freon-12 centrifugal cold water machine set |
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CN1330122A CN1330122A (en) | 2002-01-09 |
CN1279139C true CN1279139C (en) | 2006-10-11 |
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