CN106566476A - Environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant and filling method thereof - Google Patents

Environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant and filling method thereof Download PDF

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Publication number
CN106566476A
CN106566476A CN201610959226.3A CN201610959226A CN106566476A CN 106566476 A CN106566476 A CN 106566476A CN 201610959226 A CN201610959226 A CN 201610959226A CN 106566476 A CN106566476 A CN 106566476A
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cold
producing medium
temperature
azeotropic
mass percent
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金培耕
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Foshan Zhi Da Heat Pump Refrigeration Equipment Co Ltd
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Foshan Zhi Da Heat Pump Refrigeration Equipment Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B45/00Arrangements for charging or discharging refrigerant
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • C09K2205/122Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/34The mixture being non-azeotropic
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2345/00Details for charging or discharging refrigerants; Service stations therefor
    • F25B2345/001Charging refrigerant to a cycle

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
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  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Other Air-Conditioning Systems (AREA)

Abstract

The invention provides an environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant. The environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant comprises an R22 refrigerant, an R142b refrigerant and an R134a refrigerant, wherein the sum of mass percent concentration of components in the mixed refrigerant is 100%, the mass percent of the R22 is 60%-90%, the mass percent of the R142b is 5%-35%, and the mass percent of the R134a is 1%-10%. The environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant is free of toxicity and harm, the environment is protected, excellent thermophysical performance is achieved, the condensation temperature of the environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant can reach 80 DEG C or above, and the environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant completely meets the requirements of high-condensation-temperature refrigerating systems of a high-temperature air conditioner, a high-temperature drying heat pump and a high-temperature hot water heat pump.

Description

A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic and its filling method
Technical field
The present invention relates to refrigerant technology field, and in particular to a kind of high condensation temperature of environmentally friendly ternary non-azeotropic Cold-producing medium and its filling method.
Background technology
The composition included by cold-producing medium can be divided into 1, unitary system cryogen, and 2, mix refrigerant, unitary system cryogen comprises only one Chemical substance is planted, its thermo-physical performance parameters is invariable, e.g., the cold-producing medium such as R134a, R152a all has higher energy dose-effect Rate.
The mixture that mix refrigerant is made up of two or more cold-producing medium.According to it in gas-liquid phase equilibrium gas Whether phase is equal with the composition of liquid phase and is divided into:
Azeotropic refrigerant:What gas-liquid two-phase composition was equal during gas-liquid phase equilibrium belongs to azeotropic refrigerant (including equal Gas-liquid two-phase constitutes approximately equalised near azeotropic mixed refrigerant during weighing apparatus), 2, mixed non-azeotropic refrigerant.Constitute unequal category In mixed non-azeotropic refrigerant.
When azeotropic refrigerant evaporates under pressure and condenses, the composition of gas phase and liquid phase is constant, and can protect Hold stationary temperature.It and unitary system cryogen have approximate thermophysical property.This kind of refrigerated medium is to study and apply earliest, most Ripe cold-producing medium.
For mixed non-azeotropic refrigerant, its evaporation process in evaporimeter and condensation process within the condenser are all Non-ldeal mixing process.Both non-ldeal mixing processes cause mix refrigerant, and in refrigeration systems condensing pressure is reduced, and is steamed Pressure rise is sent out, the delivery temperature of compressor is reduced.This pressure ratio for allowing for refrigeration machine is reduced, and coefficient of refrigerating performance is improved, so as to carry The high energy efficiency of refrigeration system.
But, up to the present, also high-temperature air conditioner, high temperature can be entirely applied to without a kind of mixed non-azeotropic refrigerant The refrigeration system of the high condensation temperatures such as drying heat pump, high-temperature-hot-water heat pump.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide one kind is rational in infrastructure, easy to use one The high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic and its filling method are planted, it solves these above-mentioned problems.
The technical solution adopted in the present invention is as follows:A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, Including R22 cold-producing mediums, R142b cold-producing mediums and R134a cold-producing mediums, each component mass percent concentration in described mix refrigerant Sum is 100%, and wherein the mass percent of R22 is the mass percent of 60%~90%, R142b for 5%~35%, R134a's Mass percent is 1%~10%.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
Preferably, if there is cold-producing medium to leak, whole cold-producing mediums should be bled off, is filled as stated above again, it is ensured that each refrigeration Agent constant rate.
Preferably, cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the high condensation temperature of high-temperature-hot-water heat pump Refrigeration system in.
Beneficial effects of the present invention include:
The present invention is a kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, nontoxic, environmental protection, with excellent Good thermophysical property, its condensation temperature can reach more than 80 degrees Celsius, fully meet high-temperature air conditioner, high temperature drying heat pump, The refrigeration system of the high condensation temperature of high-temperature-hot-water heat pump.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment one:
A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, including R22 cold-producing mediums, R142b cold-producing mediums and R134a Cold-producing medium, each component mass percent concentration sum is 100% in described mix refrigerant, wherein the mass percent of R22 Mass percent for 60%, R142b is 5% for the mass percent of 35%, R134a.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
If there is cold-producing medium to leak, whole cold-producing mediums should be bled off, be filled as stated above again, it is ensured that each cold-producing medium ratio is not Become.
Cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the refrigeration of the high condensation temperature of high-temperature-hot-water heat pump In system.
Embodiment two:
A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, including R22 cold-producing mediums, R142b cold-producing mediums and R134a Cold-producing medium, each component mass percent concentration sum is 100% in described mix refrigerant, wherein the mass percent of R22 Mass percent for 90%, R142b is 5% for the mass percent of 5%, R134a.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
If there is cold-producing medium to leak, whole cold-producing mediums should be bled off, be filled as stated above again, it is ensured that each cold-producing medium ratio is not Become.
Cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the refrigeration of the high condensation temperature of high-temperature-hot-water heat pump In system.
Embodiment three:
A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, including R22 cold-producing mediums, R142b cold-producing mediums and R134a Cold-producing medium, each component mass percent concentration sum is 100% in described mix refrigerant, wherein the mass percent of R22 Mass percent for 70%, R142b is 2% for the mass percent of 28%, R134a.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
If there is cold-producing medium to leak, whole cold-producing mediums should be bled off, be filled as stated above again, it is ensured that each cold-producing medium ratio is not Become.
Cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the refrigeration of the high condensation temperature of high-temperature-hot-water heat pump In system.
Example IV:
A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, including R22 cold-producing mediums, R142b cold-producing mediums and R134a Cold-producing medium, each component mass percent concentration sum is 100% in described mix refrigerant, wherein the mass percent of R22 Mass percent for 80%, R142b is 10% for the mass percent of 10%, R134a.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
If there is cold-producing medium to leak, whole cold-producing mediums should be bled off, be filled as stated above again, it is ensured that each cold-producing medium ratio is not Become.
Cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the refrigeration of the high condensation temperature of high-temperature-hot-water heat pump In system.
Embodiment five:
A kind of high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, including R22 cold-producing mediums, R142b cold-producing mediums and R134a Cold-producing medium, each component mass percent concentration sum is 100% in described mix refrigerant, wherein the mass percent of R22 Mass percent for 66%, R142b is 1% for the mass percent of 33%, R134a.
A kind of filling method of the high condensation temperature cold-producing medium of environmentally friendly ternary non-azeotropic, comprises the steps:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
If there is cold-producing medium to leak, whole cold-producing mediums should be bled off, be filled as stated above again, it is ensured that each cold-producing medium ratio is not Become.
Cold-producing medium is mainly used in high-temperature air conditioner, high temperature drying heat pump, the refrigeration of the high condensation temperature of high-temperature-hot-water heat pump In system.
Drying heat pump application operational factor:
Principle is as follows:
Different types of mix refrigerant has different thermophysical propertys, and this will be that preferably providing for cold-producing medium is larger Leeway.For the refrigeration system of a certain fixation, under its optimal operating condition, it is desirable to which cold-producing medium must have specific ermal physics Property.The different azeotropic refrigerant of reasonable selection makes it meet this specific thermophysical property, it is possible to improve refrigeration The thermodynamic efficiency of system, so as to reach the effect of energy-conservation.
Because azeotropic refrigerant reduces can condensing pressure, and while evaporating pressure raise, so in condensation temperature In the case of constant with evaporating temperature, the pressure ratio of compressor will reduce, so that the lower power consumption of compressor.Therefore obtain same Less work(is just only needed during the refrigerating capacity of sample.The rising of evaporating pressure simultaneously can reduce the vacuum of evaporimeter, make evaporimeter more Stably work, and the reduction of condensing pressure can be such that condenser goes on a long journey in the state of safer.The refrigeration expert C.P.A of India In the paper that RORA is delivered in the 15th International Institute or Refrigeration, agree by taking azeotropic refrigerant R22/R12 (85/15) as an example This effect is determined.Due to the reduction of pressure ratio, the volumetric efficiency of compressor is improved, and refrigerating capacity increases, and the coefficient of performance is improved, Simultaneously the motor temperature of compressor is also reduced to 70.3 DEG C from 87.5 DEG C, and the temperature of electric motor starting coil drops to 58.3 from 97.3 DEG C DEG C, the safe handling to air-conditioner has played important effect.
Reduce can the delivery temperature of compressor using azeotropic refrigerant, it and the close phase of the property of cold-producing medium Close.Research has shown that the thermal capacitance of cold-producing medium is bigger or adiabatic exponent is less, then the delivery temperature of compressor is lower.Cold-producing medium The thermal capacitance of R115, R114, RC318 is all very big, and they have as the component of mix refrigerant reduces compressor exhaust temperature Ability.If azeotropic refrigerant R22/R115 (48.8/51.2) is in the case of 44 DEG C of condensation temperature, -12 DEG C of evaporating temperature, Its delivery temperature is 108 DEG C, and adopts unitary system cryogen R22, and its delivery temperature is 133 DEG C;When adopting R12 delivery temperature for 112℃。
In evaporation and condensation, temperature and gas-liquid phase composition are continually changing mixed non-azeotropic refrigerant, just because of Its temperature change in evaporimeter and condenser, realizes non-isothermal heat exchange in evaporimeter and condenser, shows it certainly The characteristics of energy saving of oneself uniqueness.
There is the mixing of each component and segregation phenomenon in phase transition process in mixed non-azeotropic refrigerant.Condensation process is height boiling The condensation of point component and the process of low boiling component dissolving.Wherein each component should release the latent heat of liquefaction of oneself and release mixing again Heat, the condensation heat for finally making unit cold-producing medium increases.And evaporation process is low boiling component desorption and high boiling component evaporation Process, now each component will also absorb corresponding heat of dissociation in addition to the respective latent heat of vaporization is absorbed, as a result make unit cold-producing medium Caloric receptivity is that refrigerating capacity increases.This is that refrigeration system increased refrigerating capacity in the case where power consumption is not increased.While cold-producing medium Refrigerating effect per unit swept volume also accordingly improve.Research shows, after mixed non-azeotropic refrigerant, refrigeration system is significantly reduced Energy consumption.
Such as R22/R114 (50/50) mixed non-azeotropic refrigerant replaces R22 to be used for heat pump, and coefficient of refrigerating performance improves 25%, R22/R11 (50/50) replaces after R12 in refrigerator, lower power consumption 20%.
Mixed non-azeotropic refrigerant is made into differentia influence non-azeotrope mixing system in phase transition process between its gas phase and liquid phase The thermodynamic property of cryogen.The gas phase occurred in phase transition process and the notable difference of the composition of liquid phase make non-azeotrope hybrid refrigeration The each component of agent is easier to mix and separates, so as to reach the purpose for adjusting mixing ratio.Some civil air conditions, in annual fortune Between the departure date, extraneous changes in environmental conditions is quite big, the air-conditioner of conventional use of unitary system cryogen, such as unitary system cryogen R22 Scope of application very little, its performance indications under a certain specific weather condition is very good.And performance refers to when weather conditions change Mark will decline.Mixed non-azeotropic refrigerant because during its phase transformation proportioning change therewith, it is stronger to the adaptability of variable parameter operation, The concentration of cold-producing medium each component can be adjusted according to weather conditions change.R22/R13B1 is such as used, in cooling in summer, with High concentration R22 is run, with the operation of high concentration R13B1 when heating in the winter time.After this mixed non-azeotropic refrigerant, air-conditioner Whole year can be run under higher thermodynamic efficiency, with significant energy-saving effect.
In addition, can realize that Lorenz is circulated using mixed non-azeotropic refrigerant, its heat absorption mean temperature is higher, and heat release is put down Temperature is relatively low, therefore with higher Carnot efficiency.When cold-producing medium works under the temperature-variable heat source for being given, in theory can be with The inverse Carnot cycle realized, for inverse circulation is kind of refrigeration cycle, the corresponding inverse Carnot cycle of Lorenz recycle ratio saves work(.
R134a proterties purposes:R134a does not contain chlorine atom, and to atmospheric ozone layer destruction is not played;With good peace Full performance(It is nonflammable, do not explode, it is nontoxic, without excitatory without corruption);The heat transfer property of R134a relatively, so refrigeration system The remodeling of system is easier.The heat transfer property of R134a is better than R12, is the substitute of R12.Therefore the consumption of cold-producing medium can be significantly Reduce.It is at normal temperatures colourless gas, is colourless transparent liquid under pressure itself.
Physical and chemical performance:
Molecular formula C2H2F4
Molecular weight 102.03
Boiling point, DEG C -26.1
Critical-temperature, DEG C 101.1
Critical pressure, Mpa 4.01
25 DEG C of Saturate liquid density, (g/cm 3) 1.207
25 DEG C of specific heat of liquid, [KJ/ (Kg DEG C)] 1.51
Solubility (in water, 25 DEG C) % 102.03-
Destruction ozone latent energy value(ODP) 0
Global warming coefficient value(GWP) 0.129
Critical density, g/cm 3 0.512
Potential, KJ/Kg 215.0 are evaporated under boiling point
Above-mentioned embodiment is the preferred embodiments of the present invention, is not the enforcement for limiting the present invention and interest field , equivalence changes and modification that all contents according to described in the present patent application scope of patent protection are made all should be included in this In bright claim.

Claims (4)

1. the high condensation temperature cold-producing medium of a kind of environmentally friendly ternary non-azeotropic, it is characterised in that:Including R22 cold-producing mediums, R142b Cold-producing medium and R134a cold-producing mediums, each component mass percent concentration sum is 100% in described mix refrigerant, wherein R22 Mass percent for 60%~90%, R142b mass percent for 5%~35%, R134a mass percent be 1%~10%.
2. the filling method of the high condensation temperature cold-producing medium of a kind of environmentally friendly ternary non-azeotropic, it is characterised in that including as follows Step:
The first step, refrigeration system leak detection,
Second step, after refrigeration system leak detection is qualified, vacuumizes and guarantees vacuum pressure≤30Pa, and required ratio is irrigated first R142b liquid refrigerants,
3rd step, then irrigates the liquid R134a cold-producing medium of required ratio,
4th step, finally irrigates the liquid R22 cold-producing medium of required ratio.
3. the filling method of the high condensation temperature cold-producing medium of a kind of environmentally friendly ternary non-azeotropic according to claim 2, If characterized in that, there is cold-producing medium to leak, whole cold-producing mediums should be bled off, fill as stated above again, it is ensured that each cold-producing medium ratio Example is constant.
4. the high condensation temperature cold-producing medium of a kind of environmentally friendly ternary non-azeotropic according to claim 1, it is characterised in that Cold-producing medium is mainly used in high-temperature air conditioner, in high temperature drying heat pump, the refrigeration system of the high condensation temperature of high-temperature-hot-water heat pump.
CN201610959226.3A 2016-10-28 2016-10-28 Environment-friendly ternary non-azeotropic high-condensing-temperature refrigerant and filling method thereof Pending CN106566476A (en)

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CN107011865A (en) * 2017-05-09 2017-08-04 合肥天鹅制冷科技有限公司 The mix refrigerant of ultra-high temperature air conditioner
CN108826727A (en) * 2018-04-16 2018-11-16 中国科学院理化技术研究所 Mixed working medium refrigerating system capable of adjusting working medium components
CN110257013A (en) * 2019-07-16 2019-09-20 杭州艾尔柯制冷剂科技有限公司 A kind of air source water heater energy-saving refrigerant

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Application publication date: 20170419