CN101654613A - Mixed working medium and application thereof - Google Patents
Mixed working medium and application thereof Download PDFInfo
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- CN101654613A CN101654613A CN200810213639A CN200810213639A CN101654613A CN 101654613 A CN101654613 A CN 101654613A CN 200810213639 A CN200810213639 A CN 200810213639A CN 200810213639 A CN200810213639 A CN 200810213639A CN 101654613 A CN101654613 A CN 101654613A
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Abstract
The invention relates to a mixed working medium, which consists of 1,1,1,2,3,3,3-hepta fluoropropane, 1,1,1,3,3,3-hexafluoropropane and 1,1-di fluoroethane. The mixed working medium is particularly suitable to be used for a medium and high temperature heat pump system of which the condensing dew point temperature is between 70 and 100DEG C, can be directly used in the prior heat pump systems, anddoes not have safety problems such as overhigh exhaust pressure and exhaust temperature and the like. The invention also relates to a refrigerating/heating method and a heat pump system using the mixed working medium.
Description
Technical field
The present invention relates to a kind of mixing medium and the application in refrigerating/heating method or heat pump thereof.
Background technology
Heat pump techniques is by thermodynamic cycle, the low grade heat energy that can not the directly utilize (heat energy of containing in air, soil, surface water and the shallow ground water, and industrial exhaust heat, Geothermal energy, sun power etc.) grade rise to the level that can directly utilize, consuming a part of higher-grade simultaneously can (for example electric energy).Use heat pump techniques higher, thereby reduced the discharging of greenhouse gases, reduced the thermal pollution that the waste heat discharging causes than traditional type of heating efficient.In order to satisfy the requirement of industry to higher heat supply temperature, high temperature (the condensation dew-point temperature is 70-100 ℃) direction develops in the heat pump techniques forward at present.And restrict one of key factor of its development, be exactly to lack the working medium that is fit to.The employed working medium of Ceng Zuowei moderate and high temperature heat system had R11, R113, R114 etc. in the past, and they all are the CFC materials, and higher depletion of the ozone layer gesture (ODP) and Greenhouse effect (GWP) are arranged, and developed country has forbidden, and developing country also will face forbidding.
Using more working medium at present in heat pump is HCFC22 or its surrogate R407c, R410 and R134a.For the existing heat pump that uses R22, R407c and R410a, the top temperature that hot water can be provided is 50-55 ℃ (is 55-60 ℃ corresponding to the condensation dew-point temperature); And for the existing heat pump that uses R134a, the top temperature that hot water can be provided is 55-60 ℃ (is 60-65 ℃ corresponding to the condensation dew-point temperature).If further improve this temperature, not only can reduce system performance, but also the safe limit that can surpass existing heat pump because of the exhaust pressure and the exhaust temperature of working medium causes the accident.
Therefore, prior art wishes to develop a kind of working medium, and it is suitable for providing 70-100 ℃ condensation dew-point temperature, can directly be used in existing heat pump, and not have safety problems such as exhaust pressure and excessive discharge temperature.
Summary of the invention
This present situation at prior art, the present inventor has carried out deeply and extensive studies with working medium and combination thereof present known various heat pumps, after double easily acquired, cost, toxicity and the factors such as suitability in existing heat pump (compressor) of having taken all factors into consideration working medium, obtain following particular combinations, and finished the present invention thus.
That is, the present invention relates to a kind of mixing medium, it is by 1 of 1-98 quality %, 1,1,2,3,3,1 of 3-heptafluoro-propane (R227ea), 1-98 quality %, 1,1,3,3,1 of 3-HFC-236fa (R236fa) and 1-98 quality %, 1-C2H4F2 C2H4F2 (R152a) constitutes, and wherein the mass percent sum of each constituent element is 100%.
This mixing medium is a kind of non-azeotropic mixed working medium.
The mixing medium that the present invention relates to is suitable for separately or uses with suitable lubricating oil combination and as the working medium of heat pump, is particularly useful for the condensation dew-point temperature and is 70～100 ℃ moderate and high temperature heat system.
The invention still further relates to the refrigerating/heating method of utilizing this mixing medium.
The invention effect
The mixing medium that the present invention relates to has the following advantages:
1. constituent element all is HFC, so its ODP equals zero, and can not damage the ozone layer.
2. in 70-100 ℃ condensation dew-point temperature scope, exhaust pressure is no more than 26bar (absolute pressure), is lower than the exhaust pressure upper limit of conventional compressor.Therefore, mixing medium of the present invention can directly be used existing R134a or R404a compressor, need not to design new compressor for this reason, reduces operation and use cost thus.
3. the single-stage cycle performance is good.Under the regulation operating mode of the condensate depression of 30 ℃ evaporation dew-point temperatures, 90 ℃ condensation dew-point temperature, 10 ℃ of superheating temperature and 2 ℃, exhaust temperature is up to about 120 ℃, surpasses the exhaust temperature upper limit of conventional compressor.Therefore, mixing medium of the present invention can directly be used existing compressor, and need not to take specially special measure to reduce this exhaust temperature, reduces operation and use cost thus.
4. temperature glide is little.Reduce the influence of leaking thus greatly to the mixing medium change of component.Therefore, even the part gas phase refrigerant leakage in the heat pump, great changes will take place for component, annotates as long as replenish, and need not to fill again whole working medium.
5. the volume heating capacity is big.Therefore, under identical heating capacity, can reduce the size of compressor, thereby reduce the heat-pump apparatus cost.
6. each constituent element obtains easily, and is with low cost, and toxicity is extremely low.
Embodiment
The present invention relates to a kind of mixing medium, its constituent element constitutes: 1,1 of 1-98 quality %, 1,2,3,3,1,1 of 3-heptafluoro-propane (R227ea), 1-98 quality %, 1,3,3,1 of 3-HFC-236fa (R236fa) and 1-98 quality %, 1-C2H4F2 C2H4F2 (R152a), wherein the mass percent sum of each constituent element is 100%.
The basic parameter of each constituent element is as shown in table 1.
Table 1
| Refrigeration agent | Critical temperature ℃ | Emergent pressure bar | Molar mass | Boiling point ℃ | ??ODP | ??GWP | Toxicity/combustibility |
| ??R227ea | ??101.65 | ??29.26 | ??170.03 | ??-16.45 | ??0 | ??3500 | ??A1 |
| ??R236fa | ??124.92 | ??32.00 | ??152.04 | ??-1.44 | ??0 | ??9400 | ??A1 |
| ??R152a | ??113.50 | ??44.94 | ??66.10 | ??-24.70 | ??0 | ??120 | ??A2 |
The mixing medium that the present invention relates to is applicable to provides 70-100 ℃ condensation dew-point temperature, and preferred 80-100 ℃, and further preferred 90-100 ℃.
In preferred embodiments, mixing medium of the present invention is by 1,1,1,2 of 1-98 quality %, 3,3,1,1,1,3 of 3-heptafluoro-propane, 1-98 quality %, 3,1 of 3-HFC-236fa and 1-60 quality %, the 1-C2H4F2 C2H4F2 constitutes, and wherein, the mass percent sum of each constituent element is 100%.This mixing medium is applicable to provides 80-90 ℃ condensation dew-point temperature.
In its further preferred embodiment, the present invention relates to one of following particular combinations (wherein % refers to quality %, and the mass percent sum of each constituent element is 100% in every kind of combination):
R227ea/R236fa/R152a＝1-98％/1-98％/1-30％；
R227ea/R236fa/R152a=1-60%/1-68%/greater than 30-40%;
R227ea/R236fa/R152a=1-50%/5-58%/greater than 40-45%;
R227ea/R236fa/R152a=1-45%/5-54%/greater than 45-50%;
R227ea/R236fa/R152a=1-30%/25-49%/greater than 50-55%; Perhaps
R227ea/R236fa/R152a=1-14%/26-44%/greater than 55-60%.
In the context of the invention, for example, numerical range " greater than 30-40% " and " 30-40%, but do not comprise end points 30% " synonym.The also similar understanding of other numerical ranges.
In other embodiment preferred, mixing medium of the present invention is by 1,1 of 1-42 quality %, 1,2,3,3,1,1 of 3-heptafluoro-propane, 48-98 quality %, 1,3,3,1 of 3-HFC-236fa and 1-27.7 quality %, the 1-C2H4F2 C2H4F2 constitutes, and wherein, the mass percent sum of each constituent element is 100%.This mixing medium is applicable to provides 90-100 ℃ condensation dew-point temperature.
In its further preferred embodiment, the present invention relates to one of following particular combinations (wherein % refers to quality %, and the mass percent sum of each constituent element is 100% in every kind of combination):
R227ea/R236fa/R152a＝1-42％/48-98％/1-10％；
R227ea/R236fa/R152a=1-30%/55-88%/greater than 10-15%;
R227ea/R236fa/R152a=1-20%/60-84%/greater than 15-20%;
R227ea/R236fa/R152a=1-8%/67-78%/greater than 20-25%; Perhaps
R227ea/R236fa/R152a=1-4%/70-73%/greater than 25-27.7%.
Mixing medium of the present invention can use with other additive combinations of lubricating oil or routine, perhaps itself contains this lubricating oil or additive as one of component.
These lubricating oil or additive use by its conventional amount used, have no particular limits.
As described lubricating oil, such as enumerating synthetic ester lubricant (POE is such as the EAL Arctic 22CC of Mobil) or polyalkylene glycol (PAG) class lubricating oil.
As required, in the scope of not damaging beneficial effect of the present invention, can further include in the described mixing medium and be selected from following in the constituent element more than one of adding: methylene fluoride (R32), pentafluoride ethane (R125), 1,1,1-Halothane (R143a), propylene (R1270), propane (R290), octafluoropropane (R218), butane (R600), Trimethylmethane (R600a), 1,1,1,2,3,3-HFC-236fa (R236ea) and 1,1,1,3,3-pentafluoropropane (R245fa).
These add constituent element can be to introduce with the form of impurity, also can be to have a mind to add, and in order to the actual use properties of fine setting mixing medium of the present invention, to satisfy actual particular demands, does not add constituent element but preferably do not add these.
When adding, these additions that add constituent element account for below the 5 quality % of mixing medium total mass of the present invention.
The preparation method of mixing medium of the present invention is, each constituent element material (and optional described lubricating oil, additive or add constituent element etc.) is carried out physical mixed at normal temperatures by specified quality proportioning.
Mixing medium of the present invention can be applied to the moderate and high temperature heat system of any routine, but does not comprise the fractional condensation type heat pump system, in addition not special restriction.
This moderate and high temperature heat system is the steam compression type recycle system, is made up of compressor, condenser, throttling element and vaporizer etc., also can comprise supercooler, oil separator and vapour liquid separator etc.The principle of work of this moderate and high temperature heat system below is described.
At first, the liquid mixing medium of low pressure (such as mixing medium of the present invention) has absorbed the heat of low-temperature heat source (water or air) in vaporizer, flash to low area overheat gas with the temperature that is lower than low-temperature heat source, has finished process of refrigeration.Because temperature glide, employed here vaporizer is not " full liquid type " vaporizer.Then, come from this low area overheat gas of vaporizer, be collapsed into high pressure superheater gas through compressor.This high pressure superheater gas gives high temperature heat source (water or air) to satisfy heat demand (this heat supply temperature depends on the condensation dew-point temperature of working medium) heat release in condenser, and self then is condensed into highly pressurised liquid.Subsequently, this highly pressurised liquid is through the gas-fluid two-phase mixture of throttling element throttling becoming low-temp low-pressure.At last, the gas-fluid two-phase mixture of this low-temp low-pressure after the throttling enters the aforementioned evaporation device, has finished the circulation of one-period thus.
As the moderate and high temperature heat system that can use mixing medium of the present invention, can exemplify out water source or air source high-temperature heat pump hot-water system (such as middle-size and small-size high temperature heat pump water-heater, to satisfy the needs of hotel Saunas or family life hot water, perhaps large high-temperature heat-pump hot-water unit, so that for industrial production provides a large amount of hot water, for example can be used for the heating crude oil in oil field or the like) and water source or air source high-temperature heat pump air heating system (such as middle-size and small-size drying machine, as be used for the clothes-drying machine of family or laundry, perhaps medium-and-large-sized drying plant, as desiccated wood, cloth silks and satins of tealeaves or printing and dyeing mill or the like) etc., wherein the water source also can replace with other liquid heat transmission mediums, air source also can replace with other gaseous state heat transmission mediums, and high-temperature air conditioner (a kind of air-conditioning system that can work under hot environment for example is used for the air-conditioning of desert area or air-conditioning of steelshop overhead traveling crane wheel house or the like).
According to heat pump of the present invention, 70～100 ℃ condensation dew-point temperature (preferred 80～100 ℃, and further preferred 90～100 ℃) can be provided, therefore can satisfy industrial demand fully to higher heat supply temperature.
Mixing medium of the present invention as required, can be used in combination with aforesaid lubricating oil, and have no particular limits when being applied to this heat pump.
Mixing medium of the present invention can be used as refrigerating/heating working medium and is used for the refrigerating/heating method.According to this method, make mixing medium matter of the present invention evaporation and reach refrigeration, perhaps make mixing medium condensation of the present invention and reach and heat, perhaps reach the refrigerating/heating circulation by the combination aforementioned process.
In addition, the invention still further relates to heat pump, it is a refrigerating/heating working medium with aforementioned mixing medium of the present invention.
In described refrigerating/heating method and described heat pump, as required, mixing medium of the present invention and lubricating oil can be used in combination.
Embodiments of the present invention and embodiment below are described, certainly, the present invention is not limited to these modes, can suitably implement after changing in the scope that does not break away from technical scope of the present invention.
Embodiment
Being filled into the working medium of embodiment and comparative example with ZB92KCE totally enclosed screw compressor (manufacturing of Ai Mosheng company) respectively is in the test set of core, its performance of test under the regulation operating mode, the lubricating oil of this compressor uses the EAL Arctic 22CC of Mobil.
In this manual, first kind of recommendation array mode with reference to regulation in the table 1 of GB/T5773-2004 " positive displacement refrigerant compressor method for testing performance ", be method A+ method (F, G, K), every performance of test implementation example and comparative example working medium (corresponding to refrigeration agent alleged in this standard), and calculate its parameters according to following calculating formula.
Compression ratio=discharge pressure/suction pressure,
Wherein:
Exhaust pressure (bar): locate to utilize pressure transmitter directly to measure in exhaust outlet of compressor (or condenser inlet).
Pressure of inspiration(Pi) (bar): locate to utilize pressure transmitter directly to measure in compressor air suction mouth (or evaporator outlet).
Exhaust temperature (℃): directly measure at the exhaust outlet of compressor place with temperature sensor.
Heating efficiency=quality heating capacity/quality power consumption,
Wherein:
Quality heating capacity (kJ/kg)=heating capacity/mixing medium mass rate,
Wherein heating capacity utilizes method G to measure, and the mixing medium mass rate utilizes method F to measure,
Quality power consumption (kJ/kg)=compressor power/mixing medium mass rate.
Wherein, compressor power utilizes resistance dynamometer to measure.
Volume heating capacity (kJ/m
3)=quality heating capacity/compressor air-discharging amount.
Wherein, the compressor air-discharging amount obtains by the volumetric flow rate of directly measuring the compressor air suction mouth.
Boiling point (℃): represent with the dew-point temperature under 1 normal atmosphere.
Superheating temperature (℃)=temperature out of bubble point temperature-condenser in the condenser.
Condensate depression (℃)=dew-point temperature in the suction temperature-vaporizer of vaporizer.
The condensing temperature slippage (℃)=the interior interior bubble point temperature of dew-point temperature-condenser of condenser.
The vaporization temperature slippage (℃)=inlet temperature of dew-point temperature-vaporizer in the vaporizer.
ODP * this constituent element of each constituent element of ODP=∑ of mixing medium is shared mass percent in this mixing medium is overall,
GWP * this constituent element of each constituent element of GWP=∑ of mixing medium is shared mass percent in this mixing medium is overall,
Wherein, the GWP of each constituent element and ODP see Table 1.
Embodiment 1-10
With 1,1,1,2,3,3,3-heptafluoro-propane (R227ea), 1,1,1,3,3,3-HFC-236fa (R236fa) and 1,1-C2H4F2 C2H4F2 (R152a) carries out physical mixed according to the composition proportioning of table 2 under liquid phase, make the mixing medium of embodiment of the invention 1-10, and in the regulation operating mode be respectively: 80 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 30 ℃ the condition, the results are shown in Table 2.
Comparative example 1 and 2
With R134a (1,1,1, the 2-Tetrafluoroethane, pure compound) as a comparative example 1, and with heat pump fluid R114 (Freon 114, pure compound) commonly used at present as a comparative example 2, and in the regulation operating mode be respectively: 80 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 30 ℃ the condition, the results are shown in Table 2.
Embodiment 11-28
With 1,1,1,2,3,3,3-heptafluoro-propane (R227ea), 1,1,1,3,3,3-HFC-236fa (R236fa) and 1,1-C2H4F2 C2H4F2 (R152a) carries out physical mixed according to the composition proportioning of table 3 under liquid phase, make the mixing medium of embodiment of the invention 11-28, and in the regulation operating mode be respectively: 90 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 30 ℃ the condition, the results are shown in Table 3.
Comparative example 3 and 4
With R134a as a comparative example 3, with R114 as a comparative example 4, and in the regulation operating mode be respectively: 90 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 30 ℃ the condition, the results are shown in Table 3.
Embodiment 29-41
With 1,1,1,2,3,3,3-heptafluoro-propane (R227ea), 1,1,1,3,3,3-HFC-236fa (R236fa) and 1,1-C2H4F2 C2H4F2 (R152a) carries out physical mixed according to the composition proportioning of table 4 under liquid phase, make the mixing medium of embodiment of the invention 29-41, and in the regulation operating mode be respectively: 100 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 40 ℃ the condition, the results are shown in Table 4.
Comparative example 5 and 6
With R134a as a comparative example 5, with R114 as a comparative example 6, and in the regulation operating mode be respectively: 100 ℃ of condensation dew-point temperatures, 10 ℃ of superheating temperature, 2 ℃ of condensate depression and evaporation dew-point temperature are its performance of test under 40 ℃ the condition, the results are shown in Table 4.
Result by the contrast embodiment of the invention and comparative example is as can be known clear and definite, mixing medium of the present invention is suitable for providing 70-100 ℃ condensation dew-point temperature, and can directly be used in existing heat pump, and not have safety problems such as exhaust pressure and excessive discharge temperature.
Though abovely the present invention is had been described in detail, it is to be noted that various distortion are apparent to those skilled in the art by embodiment.Therefore, these distortion should comprise in the present invention, unless these distortion have exceeded scope of the present invention.
Claims (15)
1. a mixing medium is characterized in that, by 1 of 1-98 quality %, 1,1,2,3,3,1 of 3-heptafluoro-propane (R227ea), 1-98 quality %, 1,1,3,3,1 of 3-HFC-236fa (R236fa) and 1-98 quality %, 1-C2H4F2 C2H4F2 (R152a) constitutes, wherein, the mass percent sum of each constituent element is 100%.
2. the mixing medium of claim 1 is characterized in that, this mixing medium is by 1 of 1-98 quality %, 1,1,2,3,3,1 of 3-heptafluoro-propane (R227ea), 1-98 quality %, 1,1,3,3,1 of 3-HFC-236fa (R236fa) and 1-60 quality %, 1-C2H4F2 C2H4F2 (R152a) constitutes, wherein, the mass percent sum of each constituent element is 100%.
3. the mixing medium of claim 2 is characterized in that, it is one of following that the composition of this mixing medium is selected from:
R227ea/R236fa/R152a＝1-98％/1-98％/1-30％；
R227ea/R236fa/R152a=1-60%/1-68%/greater than 30-40%;
R227ea/R236fa/R152a=1-50%/5-58%/greater than 40-45%;
R227ea/R236fa/R152a=1-45%/5-54%/greater than 45-50%;
R227ea/R236fa/R152a=1-30%/25-49%/greater than 50-55%; Perhaps
R227ea/R236fa/R152a=1-14%/26-44%/greater than 55-60%;
Wherein, the mass percent sum of each constituent element is 100% in each case.
4. the mixing medium of claim 1 is characterized in that, this mixing medium is by 1 of 1-42 quality %, 1,1,2,3,3,1 of 3-heptafluoro-propane (R227ea), 48-98 quality %, 1,1,3,3,1 of 3-HFC-236fa (R236fa) and 1-27.7 quality %, 1-C2H4F2 C2H4F2 (R152a) constitutes, wherein, the mass percent sum of each constituent element is 100%.
5. the mixing medium of claim 4 is characterized in that, it is one of following that the composition of this mixing medium is selected from:
R227ea/R236fa/R152a＝1-42％/48-98％/1-10％；
R227ea/R236fa/R152a=1-30%/55-88%/greater than 10-15%;
R227ea/R236fa/R152a=1-20%/60-84%/greater than 15-20%;
R227ea/R236fa/R152a=1-8%/67-78%/greater than 20-25%; Perhaps
R227ea/R236fa/R152a=1-4%/70-73%/greater than 25-27.7%;
Wherein, the mass percent sum of each constituent element is 100% in each case.
6. each mixing medium of claim 1-5 is characterized in that, also comprises lubricating oil.
7. the mixing medium of claim 6 is characterized in that, described lubricating oil is selected from any in synthetic ester lubricant and the polyalkylene glycols lubricating oil.
8. each the application of mixing medium in heat pump of claim 1-7.
9. the application of claim 8 is characterized in that, described this heat pump is for providing the moderate and high temperature heat system of 70～100 ℃ condensation dew-point temperature.
10. the application of claim 9 is characterized in that, this heat pump is for providing the moderate and high temperature heat system of 90～100 ℃ condensation dew-point temperature.
11. claim 8,9 or 10 application is characterized in that described mixing medium and lubricating oil are used in combination.
12. refrigerating/heating method, it is characterized in that, comprise make claim 1-7 each mixing medium matter evaporation and reach refrigeration, each mixing medium condensation and reaching of claim 1-7 is heated, perhaps reach the refrigerating/heating circulation by the combination aforementioned process.
13. a heat pump is characterized in that, is refrigerating/heating working medium with each mixing medium of claim 1-7.
14. the heat pump of claim 13 is characterized in that, described mixing medium and lubricating oil are used in combination.
15. the heat pump of claim 13, it is characterized in that described heat pump is selected from any in water source high-temperature heat pump hot-water system, air source high-temperature heat pump hot-water system, water source high-temperature heat pump air heating/cooling system, air source high-temperature heat pump air heating/cooling system and the high-temperature air conditioner system.
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|---|---|---|---|
| CN200810213639A CN101654613A (en) | 2008-08-20 | 2008-08-20 | Mixed working medium and application thereof |
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| CN200810213639A CN101654613A (en) | 2008-08-20 | 2008-08-20 | Mixed working medium and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2008
- 2008-08-20 CN CN200810213639A patent/CN101654613A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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