CN101735772B - Novel environment friendly refrigerating fluid - Google Patents
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- CN101735772B CN101735772B CN2009102608256A CN200910260825A CN101735772B CN 101735772 B CN101735772 B CN 101735772B CN 2009102608256 A CN2009102608256 A CN 2009102608256A CN 200910260825 A CN200910260825 A CN 200910260825A CN 101735772 B CN101735772 B CN 101735772B
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Abstract
The invention relates to a novel environment friendly refrigerating fluid which is prepared by 1,1-difluoroethane, difluoromethane, pentafluoroethane and carbureted hydrogen component, the carbureted hydrogen component is formed by choosing one or more than one of iso-butane, n-butane, dimethylmethane and propene with arbitrary proportion, and all components are as follows by mass percent: 5-98 percent of 1,1-difluoroethane, 1-60 percent of difluoromethane, 0-30 percent of pentafluoroethane, and 1-20 percent of the carbureted hydrogen component; the ODP value of the refrigerating fluid is zero without damaging atmospheric ozone layer, and compared with HCFC-22 and the existing substitution R407 and R410A, the GWP value is greatly reduced and the environment protecting performance is better; in addition, the charging amount is reduced, the energy efficiency ratio is improved, resource is saved, the novel environment friendly refrigerating fluid can be used as long-term substituent for HCFC-22.
Description
The present patent application is that application number is 200810082668X, the applying date to be that on February 25th, 2008, invention and created name are divided an application for " a kind of novel environment friendly refrigerating fluid ".Original application has required right of priority, as applying date in first to file of basis for priority be on November 09th, 2007, application number is 200710156803.6, formerly application country is Chinese.
Technical field
The present invention relates to a kind of refrigeration agent, relate in particular to that a kind of system is substantially constant for the equipment such as refrigeration, air-conditioning, heat pump directly substitute HCFC-22, destroy the environment friendly refrigerating fluid that atmospheric ozone potential is zero, Greenhouse effect are low, for whole world reply climate warming provides a kind of being easy to apply, the robust techniques that takes effect fast.
Technical background
HCFC-22 is owing to have good physical chemistry and thermomechanical property and good safety in utilization, economy, become most widely used in the domestic and international refrigerating and air conditioning industry, the classic refrigeration agent of over-all properties, but HCFC-22 has higher GWP (global warming potential) value and ODP (ozone depletion potential) value, not friendly to the environment is the material that is required that time limit is eliminated.
The substitute of present most popular HCFC-22 is R410A and R407C, but they have again certain defect separately, the thermal conduction that is R407C is relatively poor, refrigerating effect per unit swept volume under nominal condition and COP value are all less than HCFC-22, in order to reach the refrigerating duty identical with HCFC-22, the heat-transfer effect that needs the enhanced heat exchange device, manufacturing cost will increase; And the evaporating pressure of R410A, condensing pressure and volume refrigerating capacity compressor are all much larger than HCFC-22, can not directly be used for substituting HCFC-22, will redesign compressor, interchanger, pipeline and system in use.Because these two kinds of mix refrigerants still have improvements on performance, especially it has higher GWP value (Greenhouse effect value), and therefore R410A even more taller than the GWP value of HCFC-22 also is not desirable HCFC-22 surrogate.
Except R410A and R407C, also the HCFC-22 surrogate has been carried out a large amount of research both at home and abroad, mainly as follows:
1) publication number is the patent of invention of CN1055300C and CN1244663C, adopt the tertiary mixture of HFC-32, HFC-125 and HFC-152a as the surrogate of HCFC-22, have the thermal performance close with HCFC-22, but unresolved under long-time running, the compatibility problem of this Substitute Working Medium and HCFC-22 compressor and lubricating oil.
2) patent of invention of publication number CN1412266A, the mixture replacing HCFC-22 of employing HFC-32, HFC-134a and HFC-143a; The patent of invention of publication number CN1136065A, the mixture replacing HCFC-22 of employing HFC-32, HFC-125 and HFC-227ea; CN1189525A adopts the mixture replacing HCFC-22 of HFC-32, HFC-134a and HFC-227ea, but all has the higher problem of GWP value.
3) patent of invention of publication number CN1173525A, the mixture replacing HCFC-22 of employing HC-290, HC-600a and TS fire retardant; The patent of invention of publication number CN1255502C adopts the mixture replacing HCFC-22 of HC-1270, FC-13I1 and HC-170, and such mixture as main body, has the hidden danger of optical haze effect with hydrocarbon polymer and composition thereof, might cause new environmental problem.
4) patent of invention of publication number CN1189525A has also adopted the mixture replacing HCFC-22 of HFC-32, HFC-134a, HFC-152a and FC-13I1; The patent of invention of publication number CN1255502C has adopted the mixture replacing HCFC-22 of FC-13I1, HFC-134a and CO2, such mixture has adopted FC-13I1, have better environmental performance and thermal performance, but because iodine (I) can not synthetic, so that FC-13I1 is expensive, use cost is high, is unfavorable for being widely used.
5) patent of invention of publication number CN1780892A, adopted the mixture replacing HCFC-22 of HFC-161, HFC-32 and HFC-125, but this surrogate can not use compressor and the lubricating oil of HCFC-22, must use compressor and the ester class oil of R407C or R410A, alternative cost is high, is not suitable for directly substituting in the system of HCFC-22 using.
6) also having the part invention is that the method that adopts HCFC-22 and other materials to mix substitutes HCFC-22, adopts HCFC-22 and HFC-152a mixture such as publication number CN1269391A; The patent of invention of publication number CN1236801A adopts the mixture of HCFC-22, HFC-152a and HFC-125; The patent of invention of publication number CN1837323A adopts the mixture of HCFC-22, HFC-152a and HCFC-124; Such surrogate all belongs to transitional surrogate, is not the long-term surrogate of HCFC-22.
Face the environmental protection new demand that day by day urgent environmental problem and ODP and GWP lay equal stress on, seek a kind of thermal performance and be not less than HCFC-22, thus environmental performance especially the GWP novel environment friendly refrigerating fluid that is better than HCFC-22 and can directly uses HCFC-22 compressor and lubricating oil to reduce alternative cost become the task of top priority.
Summary of the invention
The present invention's purpose is to provide a kind of environment friendly refrigerating fluid that meets current Ozonosphere protection and suppress the environmental requirement that global warming lays equal stress on; another object of the present invention provide a kind of have be better than HCFC-22 or thermal parameter and the thermal performance suitable with it; can directly be used in the system of HCFC-22 and lubricating oil thereof, and can be used as the refrigeration agent of the long-term surrogate of HCFC-22.
For achieving the above object, the present invention adopts following technical scheme:
A kind of novel environment friendly refrigerating fluid, this refrigeration agent is comprised of the first component, methylene fluoride (HFC-32) and hydrocarbon components basically, wherein the first component is fluoroethane (HFC-161) and 1, the combination of the one or both arbitrary proportion in the 1-C2H4F2 C2H4F2 (HFC-152a), hydrocarbon components is for being selected from one or more arbitrary proportion combinations in Trimethylmethane (HC-600a), normal butane (HC-600), propane (HC-290) and the propylene (HC-1270).
Also can add pentafluoride ethane in this refrigeration agent, namely this refrigeration agent is comprised of the first component, methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and hydrocarbon components, wherein the first component is fluoroethane (HFC-161) and 1, the combination of the one or both arbitrary proportion in the 1-C2H4F2 C2H4F2 (HFC-152a), hydrocarbon components is for being selected from one or more arbitrary proportion combinations in Trimethylmethane (HC-600a), normal butane (HC-600), propane (HC-290) and the propylene (HC-1270).
Each constituent mass per-cent is: the first component: 5%-98%; HFC-32:1%-60%; HFC-125:0%-30%; Hydrocarbon components: 1%-94%.
Preferably, described refrigeration agent is comprised of the first component, methylene fluoride (HFC-32) and hydrocarbon components, and each constituent mass per-cent is: the first component: 5%-98%; HFC-32:1%-60%; Hydrocarbon components: 1%-94%.
Perhaps, described refrigeration agent is comprised of the first component, methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and hydrocarbon components, and each constituent mass per-cent is: the first component: 5%-97%; HFC-32:1%-60%; HFC-125:1%-30%; Hydrocarbon components: 1%-93%.
Refrigeration agent of the present invention is compared with existing disclosed technology, has the following advantages:
1, environmental performance is good, and depletion potential ODP value is 0, and global warming potential GWP value meets environmental requirement more much smaller than HCFC-22.
2, thermal parameter such as evaporating pressure, condensing pressure and pressure ratio and HCFC-22 are close, and under the prerequisite that does not change the equipment major parts, unit volume heating capacity, COP value all are not less than HCFC-22.Refrigeration agent of the present invention can be directly used in the system of former use HCFC-22, and can use compressor and the lubricating oil of HCFC-22; The quality refrigerating duty is large and density is little, can reduce filling quantity, improves Energy Efficiency Ratio, has the advantage of saving resource, save energy.This refrigeration agent can be used as the long-term surrogate of HCFC-22.
Embodiment
Refrigeration agent provided by the invention, its preparation method is with fluoroethane (HFC-161) or 1,1-C2H4F2 C2H4F2 (HFC-152a), methylene fluoride (HFC-32), pentafluoride ethane (HFC-125) and hydrocarbon components namely are selected from one or more the hydrocarbon polymer combinations in Trimethylmethane (HC-600a), normal butane (HC-600), propane (HC-290) and the propylene (HC-1270), carry out physical mixed according to its corresponding proportioning 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.
Pentafluoride ethane in the said components (HFC-125), its molecular formula are CHF
2CF
3, molecular weight is 120.02, and normal boiling point is-48.1 ℃, and critical temperature is 66.2 ℃, and emergent pressure is 3.63MPa.
Methylene fluoride in the said components (HFC-32), its molecular formula are CH
2F
2, molecular weight is 52.02, and normal boiling point is-51.7 ℃, and critical temperature is 78.2 ℃, and emergent pressure is 5.78MPa.
Trimethylmethane in the said components (HC-600a), its molecular formula are CH (CH
3)
2CH
3, molecular weight is 58.12, and normal boiling point is-11.6 ℃, and critical temperature is 134.7 ℃, and emergent pressure is 3.64MPa.
Normal butane in the said components (HC-600), its molecular formula are CH
3CH
2CH
2CH
3, molecular weight is 58.12, and normal boiling point is-0.5 ℃, and critical temperature is 152.0 ℃, and emergent pressure is 3.80MPa.
Propane in the said components (HC-290), its molecular formula are CH
3CH
2CH
3, molecular weight is 44.10, and normal boiling point is-42.1 ℃, and critical temperature is 96.7 ℃, and emergent pressure is 4.25MPa.
Propylene in the said components (HC-1270), its molecular formula are CH
3CHCH
2, molecular weight is 42.08, and normal boiling point is-47.7 ℃, and critical temperature is 92.4 ℃, and emergent pressure is 4.67MPa.
The following examples are used for illustrating several embodiment of the present invention, but do not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that may comprise in claims scope.
Embodiment 1: with HFC-161, HFC-125, HFC-32, HC-600 under liquid phase by 71: 10: 14: 5 mass percent is carried out physical mixed.
Embodiment 2: HFC-161, HFC-32, the HC-600 mass percent by 75: 20: 5 under liquid phase is carried out physical mixed.
Embodiment 3: HFC-152a, HFC-32, the HC-600 mass percent by 45: 50: 5 under liquid phase is carried out physical mixed.
Embodiment 4: with HFC-152a, HFC-125, HFC-32, HC-600a under liquid phase by 35: 30: 30: 5 mass percent is carried out physical mixed.
Embodiment 5: HFC-161, HFC-32, the HC-1270 mass percent by 89: 10: 1 under liquid phase is carried out physical mixed.
Embodiment 6: HFC-152a, HFC-32, the HC-600a mass percent by 40: 20: 40 under liquid phase is carried out physical mixed.
Embodiment 7: HFC-161, HFC-32, the HC-290 mass percent by 89: 10: 1 under liquid phase is carried out physical mixed.
Embodiment 8: with HFC-152a, HFC-32, HC-290, HC-600 under liquid phase by 49: 46: 1: 4 mass percent is carried out physical mixed.
Embodiment 9: with HFC-161, HFC-32, HC-600a, HC-600 under liquid phase by 79: 16: 3: 2 mass percent is carried out physical mixed.
Embodiment 10: with HFC-161, HFC-32, HC-600a, HC-290 under liquid phase by 85: 10: 1: 4 mass percent is carried out physical mixed.
Embodiment 11: with HFC-161, HFC-32, HC-600a, HC-600, HC-290 under liquid phase by 84: 10: 1: 1: 4 mass percent is carried out physical mixed.
Embodiment 12: with HFC-161, HFC-32, HC-600a, HC-600, HC-290, HC-1270 under liquid phase by 80: 15: 1: 2: 1: 1 mass percent is carried out physical mixed.
Embodiment 13: with HFC-161, HFC-32, HFC-152a, HC-600 under liquid phase by 70: 20: 5: 5 mass percent is carried out physical mixed.
Embodiment 14: HFC-161, HFC-32, the HC-600 mass percent by 98: 1: 1 under liquid phase is carried out physical mixed.
Embodiment 15: HFC-161, HFC-32, the HC-290 mass percent by 5: 1: 94 under liquid phase is carried out physical mixed.
Embodiment 16: HFC-152a, HFC-32, the HC-600 mass percent by 15: 25: 60 under liquid phase is carried out physical mixed.
Comparative Examples 1: HFC-161, HFC-152a, the HC-600 mass percent by 15: 75: 10 under liquid phase is carried out physical mixed.
Comparative Examples 2: with HFC-125, HFC-134a, HFC-161, HC-600a under liquid phase by 10: 10: 50: 30 mass percent is carried out physical mixed.
Comparative Examples 3: with HCFC-22, HCFC-124, HFC-161, HC600 under liquid phase by 60: 15: 20: 5 mass percent is carried out physical mixed.
Now the performance of above-described embodiment and HCFC-22 and Comparative Examples 1～3 are compared, characteristics of the present invention and effect are described.
1) environmental performance:
Table 1 has compared the environmental performance of above-described embodiment and HCFC-22.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 1 comparison of environmental performance
| Working medium | ODP | GWP |
| Embodiment 1 | 0 | 454 |
| Embodiment 2 | 0 | 145 |
| Embodiment 3 | 0 | 394 |
| Embodiment 4 | 0 | 1297 |
| Embodiment 5 | 0 | 78 |
| Embodiment 6 | 0 | 193 |
| Embodiment 7 | 0 | 78 |
| Embodiment 8 | 0 | 372 |
| Embodiment 9 | 0 | 118 |
| Embodiment 10 | 0 | 79 |
| Embodiment 11 | 0 | 79 |
| Embodiment 12 | 0 | 112 |
| Embodiment 13 | 0 | 150 |
| Embodiment 14 | 0 | 19 |
| Embodiment 15 | 0 | 26 |
| Embodiment 16 | 0 | 429 |
| Comparative Examples 1 | 0 | 97 |
| Comparative Examples 2 | 0 | 505 |
| Comparative Examples 3 | 0.033 | 1181 |
| HCFC-22 | 0.050 | 1810 |
| R407C | 0 | 1800 |
| R410A | 0 | 2100 |
As can be seen from Table 1, Ozone depletion potential (ODP) value of above-described embodiment is zero, atmospheric ozone layer is not had destruction, and the ODP value of Comparative Examples 3 is 0.033, does not meet environmental requirement.
Moreover; the global warming potential of above-described embodiment (GWP) value is all less than HCFC-22; it is slightly large to remove embodiment 4; for the HCFC-22GWP value 71.7% beyond; the GWP value of all the other embodiment only is 1.05%～25.2% of HCFC-22GWP value; much smaller than the GWP value of HCFC-22, with Comparative Examples 1,2 suitable, more meet current Ozonosphere protection, reduce the environmental protection requirement that the Global warming effect is laid equal stress on.
2) thermal parameter and thermal performance
Under the standard air conditioning condition (being vaporization temperature=7.2 ℃, condensing temperature=54.4 ℃, suction temperature=35 ℃, supercooling temperature=46.1 ℃), the thermal parameter of above-described embodiment and HCFC-22 (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 heating capacity q
0, relative unit volume heating capacity q
v, relative unit volume wasted work amount w
v) relatively see Table 2.
Above-mentioned relative thermal performance refers to the ratio of each embodiment thermal performance and HCFC-22 thermal performance, the relative fluid density when relative density refers to 25 ℃.
The comparison of table 2 thermal parameter and thermal performance
As seen from Table 2, under the standard air conditioning condition, the condensing pressure of the various embodiments described above and pressure ratio are all suitable with HCFC-22, and except embodiment 3,8, exhaust temperature all is lower than HCFC-22, can directly charge in the system of former use HCFC-22.The unit mass refrigerating duty of the various embodiments described above is all far above HCFC-22, and density this means the filling quantity that can significantly reduce systematic working medium much smaller than HCFC-22.Except embodiment 3,4,16, the COP value of all the other embodiment is all greater than HCFC-22, and therefore, these embodiment have energy-saving effect.Except embodiment 14,15, the volume refrigerating capacity compressor of all the other each embodiment all is not less than HCFC-22, and this shows can improve refrigerating speed.And the volume refrigerating capacity compressor of each embodiment all is higher than Comparative Examples 1,2,3, shows with Comparative Examples and compares, and all can improve refrigerating speed.
Claims (2)
1. a novel environment friendly refrigerating fluid is characterized in that each constituent mass per-cent of described refrigeration agent is: 1,1-C2H4F2 C2H4F2: 49%; Methylene fluoride: 46%; Propane: 1%; Normal butane: 4%.
2. a novel environment friendly refrigerating fluid is characterized in that each constituent mass per-cent of described refrigeration agent is: fluoroethane: 79%; Methylene fluoride: 16%; Trimethylmethane: 3%; Normal butane: 2%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102608256A CN101735772B (en) | 2007-11-09 | 2008-02-25 | Novel environment friendly refrigerating fluid |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101568036A CN101157849A (en) | 2007-11-09 | 2007-11-09 | Environment-friendly type refrigerant |
| CN200710156803.6 | 2007-11-09 | ||
| CN2009102608256A CN101735772B (en) | 2007-11-09 | 2008-02-25 | Novel environment friendly refrigerating fluid |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810082668XA Division CN101235275B (en) | 2007-11-09 | 2008-02-25 | Environmental protection type refrigerant |
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| Publication Number | Publication Date |
|---|---|
| CN101735772A CN101735772A (en) | 2010-06-16 |
| CN101735772B true CN101735772B (en) | 2013-03-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126410A (en) * | 2020-09-25 | 2020-12-25 | 珠海格力电器股份有限公司 | Mixed refrigerant, preparation method and application thereof, and automobile air conditioning system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925248A (en) * | 2016-04-29 | 2016-09-07 | 成都蓉阳科技有限公司 | Environment-friendly mixed refrigerant used for substituting dichlorofluoromethane |
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| CN1789367A (en) * | 2005-12-09 | 2006-06-21 | 西安交通大学 | Multi-element mixed working substance adapted to double temperature preparation of single-unit vapor compression type refrigerator |
| CN1810914A (en) * | 2006-01-13 | 2006-08-02 | 西安交通大学 | Multicomponent mixture work medium suitable for fractional condensation type heat pump circulation system |
| CN101003722A (en) * | 2006-10-11 | 2007-07-25 | 浙江蓝天环保高科技股份有限公司 | Quadreple mixing working medium in use for heat pump |
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| US6274062B1 (en) * | 1996-10-07 | 2001-08-14 | James B. Tieken | Halocarbon/hydrocarbon refrigerant blend |
| WO2002026913A2 (en) * | 2000-09-27 | 2002-04-04 | Honeywell International Inc. | Fluorocarbon refrigerant compositions |
| CN1789367A (en) * | 2005-12-09 | 2006-06-21 | 西安交通大学 | Multi-element mixed working substance adapted to double temperature preparation of single-unit vapor compression type refrigerator |
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| CN112126410A (en) * | 2020-09-25 | 2020-12-25 | 珠海格力电器股份有限公司 | Mixed refrigerant, preparation method and application thereof, and automobile air conditioning system |
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