CN1236801A - Safety-type refrigerant of ozone - Google Patents
Safety-type refrigerant of ozone Download PDFInfo
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- CN1236801A CN1236801A CN 98113220 CN98113220A CN1236801A CN 1236801 A CN1236801 A CN 1236801A CN 98113220 CN98113220 CN 98113220 CN 98113220 A CN98113220 A CN 98113220A CN 1236801 A CN1236801 A CN 1236801A
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Abstract
A safety-type ozone refrigerant features that it is a mixed working medium prepared from two or three of monochlorodifluoro methane, 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, difluoromethane, trifluoromethane and pentafluoroethane. Its advantages are less consumption of HCFC-22 to reduce the damage to ozonosphere, and high compatibility with HCFC-22 for the ability to use existing refrigerator.
Description
The present invention relates to a kind of safety-type refrigerant of ozone, particularly relate to a kind of filling type and substitute (Drop in Substitution) working medium, can be used for refrigeration or heating equipments such as air-conditioning, heat pump as monochlorodifluoromethane (HCFC-22).
In the prior art aspect the selection of refrigeration agent, because pure matter HCFC-22 is to the destruction of atmospheric ozone layer, the research and development of safety-type refrigerant of ozone has caused social extensive concern, hydrofluorocarbons (HFCs) is considered to comparatively, and ideal substitutes working medium, the not chloride atom of this compounds, its ODP (ODP)=0.Disclose among the Japanese kokai publication sho 1079-288A with methylene fluoride (HFC-32), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1, the mixture that 1-C2H4F2 C2H4F2 (HFC-152a), trifluoromethane (HFC-23), propane and dimethylether are formed is as environment friendly refrigerating fluid, its weak point is only to make up according to the characteristic of refrigeration agent, and very easily burning.Disclose with HFC-32, HFC-134a among CN 1076957 A and be selected from the formed composition of a kind of component in HFC-152a, HFC-143a, propane and the dimethylether as the alternative working medium of HCFC-22, its weak point is that the component of this refrigeration agent is to have added a spot of other component (as dimethylether) to mix on the candidate surrogate basis that AREP/JAREP determines basically, only limits to the mutual coupling to refrigeration agent and refrigeration cycle.In a word, HCFC-22 used in the prior art substitutes working medium, though its ODP=0 because the change of working medium requires corresponding refrigeration plant redesign, increases the infusion of financial resources of product innovation on the one hand greatly, cost is higher; Can't utilize established market widely of prior art and maintenance service site on the other hand, leak as refrigeration agent and can only replenish identical refrigeration agent, cause the difficulty in the maintenance, also can be unfavorable for applying of product innovation conversely.
The objective of the invention is the optimization when manufacturing and designing or improve the requirement of a certain refrigeration characteristic according to concrete refrigeration plant, a kind of safety-type refrigerant of ozone is provided, carrying out filling type for the HCFC-22 that has used in refrigeration plant substitutes, promptly do not change refrigeration modes, product structure and do not do big change, make product produce with use can with former working medium compatibility, thermal property reaches or is better than former working medium.
Purpose of the present invention can realize by following technical measures: the transitional material disable period of HCFC-22 of considering the international convention defined is the year two thousand twenty, include mixture in the mixing medium of the present invention based on HCFC-22, the mixing medium of selecting for use two or three component among HCFC-22, HFC-32, HFC-152a, HFC-134a, HFC-23, the HFC-125 to form, the vapour pressure of this mixing medium in the time of-40 ℃ is about 0.08Mpa～0.125Mpa.This mixing medium substitutes working medium as the filling type of pure matter monochlorodifluoromethane, and the optimization when its composition both can manufacture and design according to refrigeration plant determines, also can be according to adjusting for improving a certain characteristic.
Above-mentioned mixing medium comprises following several formula range (wherein per-cent is molar percentage): the 1) monochlorodifluoromethane of 70%～90% molar percentage, the methylene fluoride of 5%～25% molar percentage, 1%～10% mole
The pentafluoride ethane of per-cent; 2) monochlorodifluoromethane of 65%～95% molar percentage, the methylene fluoride of 4%～20% molar percentage, 1%～15% mole
The trifluoromethane of per-cent; 3) 1,1,1 of 65%～90% molar percentage, 2-Tetrafluoroethane, the methylene fluoride of 1%～5% molar percentage, 5%～30%
The methylene fluoride of molar percentage; 4) 1,1,1 of 60%～95% molar percentage, 2-Tetrafluoroethane, the methylene fluoride of 5%～40% molar percentage; 5) monochlorodifluoromethane of 70%～90% molar percentage, 1,1,1 of 1%～10% molar percentage, the 2-Tetrafluoroethane, 5%～
The methylene fluoride of 25% molar percentage; 6) monochlorodifluoromethane of 65%～95% molar percentage, the methylene fluoride of 5%～35% molar percentage; 7) 1,1,1 of 60%～90% molar percentage, 2-Tetrafluoroethane, the methylene fluoride of 9%～35% molar percentage, 1%～10%
The trifluoromethane of molar percentage; 8) 1,1,1 of 35%～50% molar percentage, the 2-Tetrafluoroethane, the methylene fluoride of 20%～45% molar percentage, 10%～
The pentafluoride ethane of 40% molar percentage.
According to general international standard (ASRE/T), under compressor name cooling condition (vaporization temperature te=7.2 ℃, condensing temperature tc=54.4 ℃, 1=35 ℃ of compressor air suction temperature t, supercooling temperature t4=46.1 ℃), get compressor heat insulating ability η=0.67, the theoretical refrigeration cycle of the pure matter of above-mentioned each component is simulated, the results are shown in Table 1.
The working medium performance of table 1 HCFC-22 and ODP=0 relatively
| ????HCFC | ????????????????????????????????HFC | |||||
| Code name | ????HCFC-22 | ????HFC-23 | ????HFC-32 | ????HFC-125 | ????HFC-134a | ????HFC-152a |
| Molecular formula | ????CHCLF 2 | ????CHF 3 | ????CH 2F 2 | ????CF 3CHF 2 | ????CH 2FCF 3 | ????CH 3CHF 2 |
| COP | ????2.82 | ????1.37 | ????2.72 | ????2.28 | ????2.85 | ????3.01 |
| qv(kJ/m 3) | ????3543 | ????7680 | ????5874 | ????3485 | ????2284 | ????2212 |
| t2(℃) | ????125 | ????122 | ????148 | ????91 | ????100 | ????110 |
| Pc(Mpa) | ????2.148 | ????9.418 | ????3.579 | ????2.805 | ????1.471 | ????1.314 |
| Pe(Mpa) | ????0.626 | ????3.018 | ????1.025 | ????0.837 | ????0.377 | ????0.339 |
| Pc/Pe | ????3.43 | ????3.12 | ????3.49 | ????3.35 | ????3.91 | ????3.87 |
| ????ODP | ????0.05 | ????0 | ????0 | ????0 | ????0 | ????0 |
| ????GWP | ????0.37 | ????- | ????0.16 | ????0.65 | ????0.29 | ????0.033 |
As shown in Table 1, in pure HFCs material, coefficient of performance COP the higher person, qv is more much lower than HCFC-22 for its volume refrigerating capacity compressor; Qv the higher person, its COP are again not as good as HCFC-22.The refrigeration performance that below is the pure matter of each component compares:
HFC-134a:qv is little than HCFC-22, if when replacing HCFC-22 with pure matter, need the redesign device, and system is negative pressure state when vaporization temperature is low slightly, and air makes degradation to system's internal leakage meeting, and reliability reduces.
HFC-32:qv is higher, can reduce the volume of existing refrigeration compressor, but row's temperature is high, and system pressure is also high, and working medium is inflammable.
HFC-23:qv and system pressure are very high, but COP is lower, can be used as the main component of fire-fighting medium.
HFC-125:qv and HCFC-22 are suitable, but COP is low, and row's temperature is low, and pressure is high slightly.
HFC-152a:qv and HFC-134a are suitable, the COP height, in many aspects can with the CFC-12 compatibility, but have combustibility.
According to the refrigeration performance characteristics of the pure matter of above-mentioned each component, adopt its mixing medium or its mixing medium of sneaking into HCFC-22 formation just can be reached the requirement that substitutes working medium as the HCFC-22 filling type.For this zeotrope, if omit in interchanger and ducted drag losses after, corresponding to the phase transition process under certain vapor pressure or the condensing pressure, transition temperature area can occur, promptly have " temperature glide effect " (GTE), for the constant temperature thermal source, because of reducing to cause heat exchange efficiency, reduces an end heat transfer temperature difference, but for non-isothermal thermal source and low-temperature receiver, utilize rightly efficient such as the temperature glide effect can reach, etc. heat flow density design, help the global optimization of process of refrigeration or device.
Some component in the mixing medium of the present invention has combustibility, can reduce combustibility on the basis that substitutes or improve HCFC-22 as far as possible, also can avoid flammable mixtures if desired.The adding of HFC-134a can suppress the combustibility of HFC-32 and HFC-152a.
Some component in the mixing medium is big because of polarity, immiscible with the lubricating oil that HCFC-22 is used, for the mutual solubility of improving HFC-134a and polyester lubricating oil can add HFC-32, simultaneously, because the qv of HFC-32 is bigger, under identical refrigeration capacity, can select the less compressor of free air delivery for use, to reduce filling quantity.In addition, add the molten oiliness that HFC-152a also can improve HFC-134a.The mutual solubility of each component and lubricating oil is different except that influence is lubricated in the mixing medium, also can reduce oil accumulating in interchanger simultaneously, eliminates or slows down waxization in kapillary, thereby raise the efficiency.
The present invention is further elaborated below in conjunction with steam compression type refrigeration air-conditioning and two embodiment of domestic refrigerator.
Embodiment 1
In refrigeration engineering, usually adopt the nominal cooling condition of compressor that refrigeration characteristic is assessed, it is vaporization temperature te=7.2 ℃, condensing temperature tc=54.4 ℃, 1=35 ℃ of compressor air suction temperature t, supercooling temperature t4=46.1 ℃), get compressor heat insulating ability η=67% (with reference to GB/T15765-1995, " room air conditioner with totally-enclosedmotor-compressor " or ASRE/T).This moment available compression ratio π (condensing pressure/evaporating pressure), volume refrigerating capacity compressor qv (refrigerating duty of the refrigeration agent of unit volume), coefficient of performance COP (theoretical refrigerating duty/power input) compares.Compression ratio can be weighed refrigeration round-robin degree of perfection to a certain extent, and in general, compression ratio is low more, and the limit efficiency of refrigeration cycle is high more.Volume refrigerating capacity compressor shows that greatly then under the condition that satisfies same refrigerating duty, the volume of compressor and system can reduce; Or for same compressor, cold that qv greatly then provides or heat are big more.Coefficient of performance COP represents the ratio of the power that effective refrigerating duty and compressor are imported, and this index also claims the first law of thermodynamics efficient of refrigeration cycle.
Non-azeotropic polybasic mixed working medium of the present invention is used for air-conditioning refrigeration system, when assessing according to above-mentioned standard, can adopt arithmetical mean vaporization temperature and arithmetical mean condensing temperature, theoretical cycle calculation result sees Table 2, hence one can see that, and the present invention is similar to the refrigeration capacity of HCFC-22 even slightly high, and COP and π are constant in wherein a kind of scheme that adopts multicomponent mixture work medium, and qv improves 13%, and exhaust temperature rises 3.8%.Table 2 HCFC-22 and mixing medium refrigeration agent are relatively
| ????COP | ?qv(kJ/m 3) | ??Pc(Mpa) | ????Pe(Mpa) | ???t2(℃) | Compression ratio π | |
| HCFC-22 | ????2.525 | ????3544 | ????2.15 | ????0.626 | ????131 | ????3.43 |
| Mixture | ????2.52 | ????4003 | ????2.42 | ????0.708 | ????136 | ????3.42 |
| Increase % | ????-0.2 | ????13.0 | ????12.6 | ????13.1 | ????3.8 | ????-0.3 |
Embodiment 2
When mixing medium of the present invention is used for domestic refrigerator, it is vaporization temperature te=-23.8 ℃ that nominal cooling condition is still adopted in the assessment of its refrigeration performance, condensing temperature tc=54.5 ℃, 1=32.2 ℃ of compressor air suction temperature t, supercooling temperature t4=32.2 ℃, get compressor heat insulating ability η=60% (with reference to GB9088-88 " use in refrigerator totally-enclosedmotor-compressor ").Non-azeotropic polybasic mixed working medium is adopted arithmetical mean vaporization temperature and arithmetical mean condensing temperature equally, its theoretical cycle calculation result sees Table 3, by the table in as can be known, the present invention is similar to the refrigeration capacity of CFC-12 even slightly high, though the wherein a kind of scheme pressure of inspiration(Pi) and exhaust pressure of multicomponent mixture work medium of adopting increases, but present Intensity Design still can meet the demands, and exhaust temperature reduces, and volume refrigerating capacity compressor and performance demands number average obviously improve.
Component utilized can be bought from market or produce among the present invention, and its purity should be high as far as possible, and water content, impurity, residual quantity are low as far as possible, in order to avoid the multicomponent solution that forms system has a negative impact to refrigeration performance or reliability.Table 3 CFC-12 and mixing medium refrigeration agent are relatively
| ????COP | ?qv(kJ/m 3) | ???Pc(Mpa) | ????Pe(Mpa) | ????t2(℃) | Compression ratio π | |
| CFC-12 | ????1.26 | ????724 | ????1.347 | ????0.132 | ????175 | ????10.2 |
| Mixture | ????1.28 | ????894 | ????1.784 | ????0.153 | ????168 | ????11.4 |
| Increase % | ????1.90 | ????23.5 | ????32.4 | ????15.9 | ????-4.0 | ????11.8 |
The present invention substitutes working medium as the filling type of pure matter HCFC-22, when being used for concrete refrigeration plant, at first, is keeping Energy Efficiency Ratio and coefficient of refrigerating performance COP when constant substantially, and refrigerating duty improves, and has practical value for the potential of giving full play to existing refrigeration plant; Secondly, because the compatibility of mixing medium of the present invention and HCFC-22, when existing refrigeration plant generation HCFC-22 leakage needs to replenish, no longer be subjected to the restriction of special-purpose refrigeration agent, can directly adopt above-mentioned mixing medium to carry out filling type substitutes, so that maintenance service makes product have more the market competitiveness.Moreover, the consumption of HCFC-22 reduces in the mixture of the present invention, destructiveness to atmospheric ozone layer also decreases, it is the transitional material of ideal HCFC-22 comparatively, can impel oneself at the refrigeration plant that uses the pure matter of HCFC-22 progressively to the transition of ozone safety type, China still is in developing country at present, especially is worthy to be popularized.
Claims (10)
1. a safety-type refrigerant of ozone is characterized in that by monochlorodifluoromethane, 1,1,1, and 2-Tetrafluoroethane, 1,1-C2H4F2 C2H4F2, methylene fluoride, trifluoromethane, the mixing medium that two or three component in the pentafluoride ethane is formed.
2. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: the monochlorodifluoromethane of 70%～90% molar percentage, the methylene fluoride of 5%～25% molar percentage, the pentafluoride ethane of 1%～10% molar percentage.
3. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: the monochlorodifluoromethane of 65%～95% molar percentage, the methylene fluoride of 4%～20% molar percentage, the trifluoromethane of 1%～15% molar percentage.
4. safety-type refrigerant of ozone according to claim 1, it is characterized in that forming: the monochlorodifluoromethane of 65%～90% molar percentage by following component, 1 of 1%～5% molar percentage, 1-C2H4F2 C2H4F2, the methylene fluoride of 5%～30% molar percentage.
5. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: 1,1,1 of 60%～95% molar percentage, 2-Tetrafluoroethane, the methylene fluoride of 5%～40% molar percentage.
6. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: the monochlorodifluoromethane of 70%～90% molar percentage, 1 of 1%～10% molar percentage, 1,1,2-Tetrafluoroethane, the methylene fluoride of 5%～25% molar percentage.
7. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: the monochlorodifluoromethane of 65%～95% molar percentage, the methylene fluoride of 9%～35% molar percentage.
8. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: 1,1 of 60%～90% molar percentage, 1, the 2-Tetrafluoroethane, the methylene fluoride of 9%～35% molar percentage, the trifluoromethane of 1%～10% molar percentage.
9. safety-type refrigerant of ozone according to claim 1 is characterized in that being made up of following component: 1,1 of 35%～50% molar percentage, 1, the 2-Tetrafluoroethane, the methylene fluoride of 20%～45% molar percentage, the pentafluoride ethane of 10%～40% molar percentage.
10. safety-type refrigerant of ozone according to claim 1 is characterized in that being used for steam compression type refrigeration or heating combined equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98113220 CN1236801A (en) | 1998-05-22 | 1998-05-22 | Safety-type refrigerant of ozone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98113220 CN1236801A (en) | 1998-05-22 | 1998-05-22 | Safety-type refrigerant of ozone |
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| CN1236801A true CN1236801A (en) | 1999-12-01 |
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| CN 98113220 Pending CN1236801A (en) | 1998-05-22 | 1998-05-22 | Safety-type refrigerant of ozone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313559C (en) * | 2005-12-09 | 2007-05-02 | 天津大学 | Ternary mixed working medium for intermediate-high-temperature heat pump |
| CN105838327A (en) * | 2006-03-07 | 2016-08-10 | 斯蒂弗科财产有限责任公司 | Refrigerant substitute for R-22 based refrigeration system |
| CN106152605A (en) * | 2015-04-24 | 2016-11-23 | 格林雅思株式会社 | Heat pump type refrigerating heating combined equipment, cold-producing medium and heat exchanger |
| CN110028937A (en) * | 2019-04-26 | 2019-07-19 | 中国科学院理化技术研究所 | A kind of non-combustible cool storage medium of mixing |
-
1998
- 1998-05-22 CN CN 98113220 patent/CN1236801A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313559C (en) * | 2005-12-09 | 2007-05-02 | 天津大学 | Ternary mixed working medium for intermediate-high-temperature heat pump |
| CN105838327A (en) * | 2006-03-07 | 2016-08-10 | 斯蒂弗科财产有限责任公司 | Refrigerant substitute for R-22 based refrigeration system |
| CN106152605A (en) * | 2015-04-24 | 2016-11-23 | 格林雅思株式会社 | Heat pump type refrigerating heating combined equipment, cold-producing medium and heat exchanger |
| CN110028937A (en) * | 2019-04-26 | 2019-07-19 | 中国科学院理化技术研究所 | A kind of non-combustible cool storage medium of mixing |
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