CN1330122A - 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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- CN1330122A CN1330122A CN 01120436 CN01120436A CN1330122A CN 1330122 A CN1330122 A CN 1330122A CN 01120436 CN01120436 CN 01120436 CN 01120436 A CN01120436 A CN 01120436A CN 1330122 A CN1330122 A CN 1330122A
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- Prior art keywords
- refrigerant
- cfc
- freon
- centrifugal
- c2h4f2
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- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003507 refrigerant Substances 0.000 title claims abstract description 19
- 235000019404 dichlorodifluoromethane Nutrition 0.000 title abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 5
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005057 refrigeration Methods 0.000 claims abstract description 29
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims abstract description 25
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 7
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001282 iso-butane Substances 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- LPHRYDDNVANDNB-UHFFFAOYSA-N [Cl].C(C)(F)F Chemical compound [Cl].C(C)(F)F LPHRYDDNVANDNB-UHFFFAOYSA-N 0.000 description 5
- 235000013847 iso-butane Nutrition 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 206010026865 Mass Diseases 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Abstract
一种氟利昂－12离心式冷水机组的替代制冷剂,涉及一种离心式冷水机组使用的制冷剂。该制冷剂含有一氯二氟甲烷、1,1,1,2,3,3,3－七氟丙烷和1－一氯－1,1－二氟乙烷三种物质,还可以添加异丁烷组成四元混合物。其制备方法是将上述各种组分按其相应的配比在液相下进行物理混合即可。该制冷剂不仅符合环保要求,安全、可靠、制冷效率与CFC－12相当,而且压缩机与系统中的主要部件不需改动,生产线不需改造,可直接进行充灌。在性能上还略好于氟利昂－12,可作为现有离心式冷水机组氟利昂－12的替代制冷剂。The utility model relates to an alternative refrigerant of Freon-12 centrifugal chiller, which relates to a refrigerant used in the centrifugal chiller. The refrigerant contains chlorodifluoromethane, 1,1,1,2,3,3,3-heptafluoropropane and 1-chloro-1,1-difluoroethane, and can also be composed of isobutane Quaternary mixture. Its preparation method is to physically mix the above-mentioned various components according to their corresponding proportions in the liquid phase. The refrigerant not only conforms to environmental protection requirements, but is also safe and reliable, and its refrigeration efficiency is equivalent to that of CFC-12. Moreover, the main components in the compressor and the system do not need to be changed, and the production line does not need to be modified, and it can be directly charged. It is slightly better than Freon-12 in performance, and can be used as a substitute refrigerant for Freon-12 in existing centrifugal chillers.
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 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, it is characterized in that above-mentioned refrigeration agent also contains Trimethylmethane, 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.
The specific embodiment
Cold-producing medium of the present invention, it is characterized in that by F-22 (HCFC-22), 1,1,1,2,3,3, three kinds of materials of 3-heptafluoro-propane (HFC-227ea) and 1-one chlorine-1,1-difluoroethane (HCFC-142b) form, and also can add iso-butane (HC-600a) again and form quaternary mixed refrigerant. But because the slip temperature of these two groups of mixtures is all larger, in order to satisfy the specific (special) requirements of centrifugal compressor, to dissimilar evaporimeters, such as flooded type or dry type, need the different mix refrigerants that charge proportioning.
For the centrifugal water-cooled unit of dry evaporator, the constituent content of ternary mixture (mass percent) is:
F-22: 28-30%
HFC-227ea: 60%-62%
1-one chlorine-1,1-difluoroethane: 10%-12%
For the centrifugal water-cooled unit of flooded type evaporimeter, the constituent content of ternary mixture (mass percent) is:
F-22: 14%-16%
HFC-227ea: 67%-69%
1-one chlorine-1,1-difluoroethane: 15%-17%
For the centrifugal water-cooled unit of dry evaporator, iso-butane (HC-600a) can also be added on aforementioned ternary mixture basis, to have better oil-soluble. Its constituent content (mass percent) is:
F-22: 27%-29%
HFC-227ea: 58%-60%
1-one chlorine-1,1-difluoroethane: 9%-11%
Iso-butane: 2%-4%
For the centrifugal water-cooled unit of flooded type evaporimeter, also iso-butane (HC-600a) can be added on aforementioned ternary mixture basis, to have better oil-soluble. Its constituent content (mass percent) is:
F-22: 14%-16%
HFC-227ea: 66%-68%
1-one chlorine-1,1-difluoroethane: 14%-16%
Iso-butane: 2%-3%
In order to help the understanding to invention and advantage thereof, the below enumerates several specific embodiments.
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 above-described embodiment cold-producing medium 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 |
| Delivery 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 (4)
1. the alternative refrigerant of a 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, three kinds of materials of 1-C2H4F2 C2H4F2, its component concentration (mass percent) 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. according to the alternative refrigerant of the described a kind of F-12 centrifugal refrigerating machines of claim 1, it is characterized in that each component concentration (mass percent) is respectively in the described refrigeration agent: monochlorodifluoromethane: 14%-16%1,1,1,2,3,3,3-heptafluoro-propane: 67%-69%1-one chloro-1,1-C2H4F2 C2H4F2: 15%-17%
3. according to the alternative refrigerant of the described a kind of F-12 centrifugal refrigerating machines of claim 1, it is characterized in that described refrigeration agent also contains Trimethylmethane, 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%
4. according to the alternative refrigerant of the described a kind of F-12 centrifugal refrigerating machines of claim 2, it is characterized in that described refrigeration agent also contains Trimethylmethane, its component concentration (mass percent) is 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%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120436 CN1279139C (en) | 2001-07-13 | 2001-07-13 | Substitute refrigerant for freon-12 centrifugal cold water machine set |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120436 CN1279139C (en) | 2001-07-13 | 2001-07-13 | Substitute refrigerant for freon-12 centrifugal cold water machine set |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1330122A true CN1330122A (en) | 2002-01-09 |
| CN1279139C CN1279139C (en) | 2006-10-11 |
Family
ID=4664131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01120436 Expired - Fee Related CN1279139C (en) | 2001-07-13 | 2001-07-13 | Substitute refrigerant for freon-12 centrifugal cold water machine set |
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| Country | Link |
|---|---|
| CN (1) | CN1279139C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093848A (en) * | 2009-12-11 | 2011-06-15 | 田朝嫦 | Novel high-temperature mixed refrigerant |
-
2001
- 2001-07-13 CN CN 01120436 patent/CN1279139C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093848A (en) * | 2009-12-11 | 2011-06-15 | 田朝嫦 | Novel high-temperature mixed refrigerant |
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| Publication number | Publication date |
|---|---|
| CN1279139C (en) | 2006-10-11 |
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