CN1285699C - Environmental protection type refrigerant for replacement of CFC-12 - Google Patents
Environmental protection type refrigerant for replacement of CFC-12 Download PDFInfo
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- CN1285699C CN1285699C CN 200410084844 CN200410084844A CN1285699C CN 1285699 C CN1285699 C CN 1285699C CN 200410084844 CN200410084844 CN 200410084844 CN 200410084844 A CN200410084844 A CN 200410084844A CN 1285699 C CN1285699 C CN 1285699C
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- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 title abstract description 31
- 235000019404 dichlorodifluoromethane Nutrition 0.000 title abstract description 31
- 230000007613 environmental effect Effects 0.000 title abstract description 12
- 239000003507 refrigerant Substances 0.000 title abstract description 9
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 54
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 claims abstract description 34
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005057 refrigeration Methods 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 5
- 229940051271 1,1-difluoroethane Drugs 0.000 abstract 1
- XNFQIHKNBFGKSE-UHFFFAOYSA-N [F].CC Chemical compound [F].CC XNFQIHKNBFGKSE-UHFFFAOYSA-N 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000004378 air conditioning Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
The present invention discloses an environmental protection type refrigerant for substituting CFC-12. The refrigerant contains the components by mass percentage of 1% to 50% of fluorine ethane (HFC-161), 1% to 50% of 1, 1-difluoroethane (HFC-152a), 30% to 90% of 1, 1, 1, 2-tetrafluoroethane (HFC-134a) and does not destroy the atmospheric ozone layer due to the ODP value of zero. Compared with the CFC-12 and the existing main substitute HFC-134a thereof, the refrigerant has a small GWP value and accords with the requirement of environmental protection. The working pressure and the pressure ratio of the refrigerant approach to those of the main substitute HFC-134a of the CFC-12 and the refrigerant can be directly used in an original system using the HFC-134a on the premise of no basic main part change in the system and can reduce the quantity of filling. The refrigerant can be used as a long-time substitute of the CFC-12.
Description
Technical field
The present invention relates to refrigeration agent, relate in particular to the environment friendly refrigerating fluid of a kind of CFC alternative-12.
Technical background
In Chlorofluorocarbons (CFCs) (CFC) class refrigeration agent because CFC-12 thermal property excellence, stable chemical performance, nontoxic, advantage such as do not fire, be widely used in fields such as automative air conditioning, home freezer and industrial freezer for a long time.
But, because CFC-12 has certain destruction to the ozonosphere in the atmosphere stratosphere, its depletion latent energy value ODP (Ozone Depletion Potential) value is 0.90 (with CFC-11 as benchmark value 1.0), thus " about the Montreal Agreement book of Ozone Depleting Substances " with it as first material of eliminating.At present, developed country has stopped the production of CFC-12, and China is also cutting down its turnout and usage quantity year by year, and finally stops to produce and using before 2010 except that maintenance is used comprehensively.
The substitute of CFC-12 that generally acknowledge, the consumption maximum is 1,1,1 both at home and abroad at present, 2-Tetrafluoroethane (HFC-134a).Because it has the physical properties close with CFC-12, and its ODP value is 0, so is widely used in the products such as automative air conditioning, refrigerator of new production, especially the large usage quantity of automative air conditioning.Chinese government regulation, China automobile production enterprise stopped to assemble the motorcar air conditioner of CFC-12 before 1 day January in 2002, and therefore, after 2002, the consumption of HFC-134a progressively increases, and estimates will reach 10,000 tons in 2005, will reach 20,000 tons in 2010.But there is a serious environmental problem in HFC-134a, and promptly to the Greenhouse effect of the earth, its global warming potential GWP (Global Warming Potential) value is 1300 (with CO2 as benchmark value 1.0), and the Global warming effect is bigger.Held in 1997 about preventing in the meeting of global warming capital of a country that lay special stress on will control the discharging of greenhouse gases.More and more paid attention in the world from protection ozonosphere and inhibition global warming two broad aspect comprehensive evaluation refrigeration agent environmental-protecting performances.Therefore, seek new CFC alternative-12, and the work that environmental performance and thermal property all are better than the refrigeration working medium of HFC-134a has been imperative.
Summary of the invention
The object of the present invention is to provide the environment friendly refrigerating fluid of a kind of CFC alternative-12.This refrigeration agent provided by the present invention does not only destroy atmospheric ozone layer, and Greenhouse effect are littler, meets current protection ozonosphere and suppresses the environmental requirement that global warming is laid equal stress on.In addition, also have thermal parameter and the thermal property suitable, can be used as the long-term surrogate of CFC-12 with CFC-12.
This refrigeration agent provided by the present invention is characterized in that this refrigeration agent contains fluoroethane (HFC-161), 1,1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1, and three kinds of components of 2-Tetrafluoroethane (HFC-134a), its mass percent is:
HFC-161：1％-50％
HFC-152a：1％-50％
HFC-134a：30％-90％
The mass percent of comparative optimization is:
HFC-161：5％-30％
HFC-152a：5％-30％
HFC-134a：60％-90％
Most preferred mass percent is:
HFC-161：5％-20％
HFC-152a：5％-20％
HFC-134a：70％-85％
Refrigeration agent of the present invention compared with prior art has the following advantages:
1) environmental performance is good, and not only depletion potential ODP value is 0, and global warming potential GWP value is significantly smaller than CFC-12 and main surrogate HFC-134a thereof, compliance with environmental protection requirements, and this is sharpest edges of the present invention.
2) thermal parameter such as evaporating pressure, condensing pressure and pressure ratio and CFC-12 and main surrogate HFC-134a thereof are close, substantially do not changing under the prerequisite of equipment major parts, thermal parameter such as unit mass refrigerating duty, refrigerating effect per unit swept volume are better than CFC-12 and HFC-134a, though the COP value is less than CFC-12, greater than HFC-134a.Can be directly used in the system of former use HFC-134a, and can reduce filling quantity.This refrigeration agent can be used as the long-term surrogate of CFC-12.
Embodiment
Refrigeration agent provided by the invention, its preparation method are with fluoroethane (HFC-161), 1,1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1, and three kinds of components of 2-Tetrafluoroethane (HFC-134a) are carried out physical mixed according to its corresponding mixture ratio under liquid phase state.
Fluoroethane in the said components (HFC-161), its molecular formula are CH
3CH
2F, molecular weight are 48.06, and normal boiling point is-37.1 ℃, and critical temperature is 102.2 ℃, and emergent pressure is 4.70MPa.
In the said components 1, its molecular formula of 1-C2H4F2 C2H4F2 (HFC-152a) is CH
3CHF
2, molecular weight is 66.05, and normal boiling point is-24.02 ℃, and critical temperature is 113.26 ℃, and emergent pressure is 4.52MPa.
In the said components 1,1,1, its molecular formula of 2-tetrafluoromethane (HFC-134a) is CF
3CH
2F, molecular weight are 102.03, and normal boiling point is-26.07 ℃, and critical temperature is 101.06 ℃, and emergent pressure is 4.06MPa.
Provide specific embodiments of the invention below, these embodiment only are illustrative, and limit the scope of the invention anything but.
Embodiment 1: HFC-161, HFC-152a and HFC-134a mass percent by 9: 1: 90 under liquid phase are carried out physical mixed.
Embodiment 2: HFC-161, HFC-152a and HFC-134a mass percent by 1: 9: 90 under liquid phase are carried out physical mixed.
Embodiment 3: HFC-161, HFC-152a and HFC-134a mass percent by 50: 1: 49 under liquid phase are carried out physical mixed.
Embodiment 4: HFC-161, HFC-152a and HFC-134a mass percent by 1: 50: 49 under liquid phase are carried out physical mixed.
Embodiment 5: HFC-161, HFC-152a and HFC-134a mass percent by 50: 20: 30 under liquid phase are carried out physical mixed.
Embodiment 6: HFC-161, HFC-152a and HFC-134a mass percent by 20: 50: 30 under liquid phase are carried out physical mixed.
Embodiment 7: HFC-161, HFC-152a and HFC-134a mass percent by 5: 5: 90 under liquid phase are carried out physical mixed.
Embodiment 8: HFC-161, HFC-152a and HFC-134a mass percent by 30: 10: 60 under liquid phase are carried out physical mixed.
Embodiment 9: HFC-161, HFC-152a and HFC-134a mass percent by 10: 30: 60 under liquid phase are carried out physical mixed.
Embodiment 10: HFC-161, HFC-152a and HFC-134a mass percent by 5: 30: 65 under liquid phase are carried out physical mixed.
Embodiment 11: HFC-161, HFC-152a and HFC-134a mass percent by 10: 5: 85 under liquid phase are carried out physical mixed.
Embodiment 12: HFC-161, HFC-152a and HFC-134a mass percent by 5: 10: 85 under liquid phase are carried out physical mixed.
Embodiment 13: HFC-161, HFC-152a and HFC-134a mass percent by 20: 10: 70 under liquid phase are carried out physical mixed.
Embodiment 14: HFC-161, HFC-152a and HFC-134a mass percent by 10: 20: 70 under liquid phase are carried out physical mixed.
Embodiment 15: HFC-161, HFC-152a and HFC-134a mass percent by 25: 5: 70 under liquid phase are carried out physical mixed.
Embodiment 16: HFC-161, HFC-152a and HFC-134a mass percent by 5: 25: 70 under liquid phase are carried out physical mixed.
Now the performance of the foregoing description and CFC-12 and main surrogate HFC-134a thereof are compared, characteristics of the present invention and effect are described.
A. near azeotropic
The comparison of table 1 temperature glide (unit: ℃)
| Bubble point temperature | Dew-point temperature | Temperature glide | |
| Embodiment 1 | -31.18 | -28.67 | 2.51 |
| Embodiment 2 | -26.50 | -25.94 | 0.56 |
| Embodiment 3 | -36.37 | -35.89 | 0.48 |
| Embodiment 4 | -25.22 | -24.74 | 0.48 |
| Embodiment 5 | -35.70 | -34.71 | 0.99 |
| Embodiment 6 | -31.85 | -28.86 | 2.99 |
| Embodiment 7 | -29.24 | -27.30 | 1.94 |
| Embodiment 8 | -34.71 | -32.71 | 2.00 |
| Embodiment 9 | -30.15 | -27.44 | 2.71 |
| Embodiment 10 | -28.12 | -26.22 | 1.90 |
| Embodiment 11 | -31.31 | -28.67 | 2.64 |
| Embodiment 12 | -28.98 | -27.04 | 1.94 |
| Embodiment 13 | -33.42 | -32.75 | 2.67 |
| Embodiment 14 | -30.58 | -27.86 | 2.72 |
| Embodiment 15 | -34.37 | -32.15 | 2.22 |
| Embodiment 16 | -28.31 | -26.40 | 1.91 |
(annotate: bubble point temperature in the table and dew-point temperature all are the temperature of saturation when standard atmospheric pressure 101.325kPa)
As can be seen from Table 1, the temperature glide of all embodiment is all little, and maximum is no more than 3.0 ℃, all belongs near azeotropic mixed refrigerant.
B. environmental performance
Table 2 has compared the environmental performance of the foregoing description and CFC-12, HFC-134a.Wherein as benchmark value 1.0, the GWP value is with CO with CFC-11 for the ODP value
2As benchmark value 1.0 (100 years).
Table 2 environmental performance relatively
| Refrigeration agent | ODP | GWP |
| Embodiment 1 | 0 | 1061 |
| Embodiment 2 | 0 | 1122 |
| Embodiment 3 | 0 | 415 |
| Embodiment 4 | 0 | 581 |
| Embodiment 5 | 0 | 266 |
| Embodiment 6 | 0 | 335 |
| Embodiment 7 | 0 | 1091 |
| Embodiment 8 | 0 | 581 |
| Embodiment 9 | 0 | 664 |
| Embodiment 10 | 0 | 747 |
| Embodiment 11 | 0 | 981 |
| Embodiment 12 | 0 | 1015 |
| Embodiment 13 | 0 | 732 |
| Embodiment 14 | 0 | 782 |
| Embodiment 15 | 0 | 708 |
| Embodiment 16 | 0 | 809 |
| CFC-12 | 0.9 | 8500 |
| HFC-134a | 0 | 1300 |
As can be seen from Table 2, the ozonosphere of the foregoing description consumes potential (ODP) value and is zero, and atmospheric ozone layer is not had destruction, and this point is better than CFC-12.
Moreover; the global warming potential of the foregoing description (GWP) value is also less than CFC-12, HFC-134a; have only 3～13% of CFC-12GWP value, 20～86% of HFC-134a GWP value more meets current protection ozonosphere, reduces the environmental protection requirement that the Global warming effect is laid equal stress on.
C. thermal parameter and thermal performance
Table 3 has compared under the automative air conditioning operating mode (being vaporization temperature=-1 ℃, condensing temperature=60 ℃, suction temperature=4 ℃, supercooling temperature=57 ℃), the thermal parameter of the foregoing description and CFC-12, HFC-134a (that is: evaporating pressure P
0, condensing pressure P
k, pressure ratio P
k/ P
0, exhaust temperature t
2) and relative thermal performance (that is: relatively COP, relative unit quality refrigerating duty q
0, relative unit volume refrigerating capacity compressor q
v, relative unit volume wasted work amount w
v).Said relative thermal performance is meant the ratio of each embodiment thermal performance and CFC-12 thermal performance.
The comparison of table 3 thermal parameter
| Embodiment 11 | 0.325 | 1.847 | 5.68 | 73.14 | 0.958 | 1.35 | 1.102 | 1.150 |
| Embodiment 12 | 0.301 | 1.745 | 5.79 | 73.04 | 0.963 | 1.35 | 1.046 | 1.086 |
| Embodiment 13 | 0.351 | 1.946 | 5.54 | 75.39 | 0.960 | 1.49 | 1.180 | 1.230 |
| Embodiment 14 | 0.314 | 1.788 | 5.69 | 75.00 | 0.971 | 1.48 | 1.093 | 1.125 |
| Embodiment 15 | 0.367 | 2.013 | 5.48 | 75.62 | 0.953 | 1.50 | 1.217 | 1.277 |
| Embodiment 16 | 0.293 | 1.696 | 5.80 | 74.77 | 0.981 | 1.49 | 1.039 | 1.060 |
| CFC-12 | 0.298 | 1.522 | 5.10 | 72.36 | 1.0 | 1.0 | 1.0 | 1.0 |
| HFC-134a | 0.283 | 1.682 | 5.96 | 70.82 | 0.949 | 1.22 | 0.979 | 1.026 |
As seen, under the automative air conditioning operating mode, condensing pressure, evaporating pressure and CFC-12, the HFC-134a of embodiment 1,2,4,6,7,9,10,11,12,14,16 are close, all are in allowed band from table 3; Though pressure ratio is higher than CFC-12, all be lower than HFC-134a, can directly charge in the system of former use HFC-134a.Though the exhaust temperature of the various embodiments described above all is higher than CFC-12 and HFC-134a, amplitude is less, all is in the allowed band; The unit mass refrigerating duty all is higher than CFC-12 and HFC-134a, this means the filling quantity that can reduce system refrigerant; Though the COP value a little less than CFC-12, all is higher than HFC-134a, therefore, these embodiment have energy-saving effect.The refrigerating effect per unit swept volume of embodiment 1,2,4,6,7,9,10,11,12,14,16 is compared with HFC-134a with unit volume wasted work amount, and deviation is little, and this shows that these embodiment can directly use the compressor of HFC-134a, and need not substantially to change.
Claims (3)
1, the environment friendly refrigerating fluid of a kind of CFC alternative-12 is characterized in that this refrigeration agent contains fluoroethane (HFC-161), 1,1-C2H4F2 C2H4F2 (HFC-152a) and 1,1,1, and three kinds of components of 2-Tetrafluoroethane (HFC-134a), its mass percent is:
Fluoroethane (HFC-161): 1%-50%
1,1-C2H4F2 C2H4F2 (HFC-152a): 1%-50%
1,1,1,2-Tetrafluoroethane (HFC-134a): 30%-90%.
2, the environment friendly refrigerating fluid of a kind of CFC alternative-12 according to claim 1 is characterized in that its mass percent is:
Fluoroethane (HFC-161): 5%-30%
1,1-C2H4F2 C2H4F2 (HFC-152a): 5%-30%
1,1,1,2-Tetrafluoroethane (HFC-134a): 60%-90%.
3, the environment friendly refrigerating fluid of a kind of CFC alternative-12 according to claim 1 is characterized in that its mass percent is:
Fluoroethane (HFC-161): 5%-20%
1,1-C2H4F2 C2H4F2 (HFC-152a): 5%-20%
1,1,1,2-Tetrafluoroethane (HFC-134a): 70%-85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410084844 CN1285699C (en) | 2004-09-29 | 2004-09-29 | Environmental protection type refrigerant for replacement of CFC-12 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410084844 CN1285699C (en) | 2004-09-29 | 2004-09-29 | Environmental protection type refrigerant for replacement of CFC-12 |
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| CN1629248A CN1629248A (en) | 2005-06-22 |
| CN1285699C true CN1285699C (en) | 2006-11-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014202017A1 (en) | 2013-06-21 | 2014-12-24 | 浙江蓝天环保高科技股份有限公司 | Mixed refrigerant |
| WO2015000367A1 (en) | 2013-07-05 | 2015-01-08 | 浙江蓝天环保高科技股份有限公司 | Environment-friendly near-azeotropic mixed refrigerant |
| WO2018120257A1 (en) | 2016-12-26 | 2018-07-05 | 浙江衢化氟化学有限公司 | Refrigerant composition containing hydrofluoroolefin |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460479C (en) * | 2006-07-10 | 2009-02-11 | 浙江蓝天环保高科技股份有限公司 | Environment-friendly type heat pump mixed working medium |
| CN110257014B (en) * | 2019-07-19 | 2020-10-09 | 珠海格力电器股份有限公司 | Mixed refrigeration working medium |
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2004
- 2004-09-29 CN CN 200410084844 patent/CN1285699C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014202017A1 (en) | 2013-06-21 | 2014-12-24 | 浙江蓝天环保高科技股份有限公司 | Mixed refrigerant |
| WO2015000367A1 (en) | 2013-07-05 | 2015-01-08 | 浙江蓝天环保高科技股份有限公司 | Environment-friendly near-azeotropic mixed refrigerant |
| US10752819B2 (en) | 2013-07-05 | 2020-08-25 | Zhejiang Lantian Environmental Protection Hi-Tech Co., Ltd. | Environmentally friendly near-azeotropic mixed refrigerant |
| US11136483B2 (en) | 2013-07-05 | 2021-10-05 | Zhejiang Lantian Environmental Protection Hi-Tech Co., Ltd. | Environmentally friendly near-azeotropic mixed refrigerant |
| US11549042B2 (en) | 2013-07-05 | 2023-01-10 | Zhejiang Lantian Environmental Protection Hi-Tech Co., Ltd. | Environmentally friendly near-azeotropic mixed refrigerant |
| WO2018120257A1 (en) | 2016-12-26 | 2018-07-05 | 浙江衢化氟化学有限公司 | Refrigerant composition containing hydrofluoroolefin |
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| Publication number | Publication date |
|---|---|
| CN1629248A (en) | 2005-06-22 |
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