CN101984013B - Novel environmental-protection refrigerant component for substituting 1, 1, 1, 2- tetrafluoroethane (hydrochlorofluorocarbon (HFC)-134a) - Google Patents

Abstract

The invention relates to a novel environmental-protection refrigerant for substituting 1, 1, 1, 2- tetrafluoroethane (hydrochlorofluorocarbon (HFC)-134a), which is characterized in that 50 to 56kg of propane (R-290) and 40 to 49kg of isobutene (R-600a) of hydrocarbon series are taken as a basis; 2 to 5kg of n-butane (R-600) and 1 to 3kg of propylene (R-1270) are added; and a near-azeotropic mixture refrigerant with the ozone depletion potential (ODP) of 0 and the global warming potential (GWP) of 3 is formed after 0.5 to 1kg of an additive-hexamethylene silicone oil are added for near-azeotropic.

Description

Substitute 1,1,1,2-Tetrafluoroethane environmental protection refrigerant constituent

Technical field: the present invention relates to a kind of 1,1,1,2-Tetrafluoroethane (HFC-134a) that substitutes and use the novel environment-friendly refrigerant constituent.

Background technology

Refrigeration agent (Refrigerant) refers to the startup fluid of freeze cycle, take heat by force to the general name of the carrier of high temperature from cryogenic object, main use is cheap, chemically stable, the Chlorofluorocarbons of excellent in efficiency (Chloro fluoro carbon, hereinafter to be referred as ' CFC ') and fluorochlorohydrocarbon (Hydro chloro fluoro carbon is hereinafter to be referred as ' HCFC ') and fluorine carbon (Hydro fluoro carbon is hereinafter to be referred as ' HFC ').

But depletion of the ozone layer becomes the global environment problem in the stratosphere that CFC and HCFC cause, so the production of the CFC that damages the ozone layer in the stratosphere and HCFC and use the Montreal Protocol restriction of being passed through in 1987.So it is 0.0 alternative refrigerant that the most of country in the whole world all wants to use depletion of the ozone layer index (ODP).

And the Kyoto Protocol (Kyoto Protocol) also is that 0 HFC has also stipulated in Global warming material (GWP=1,430) the restriction project with the earth's ozone layer destructing index.No matter what material, become the substitute of original refrigeration agent, at first must possess and original refrigeration agent similar performance coefficient (Coefficient of performance, C.O.P), performance and the similar refrigerating effect of original refrigeration agent, and to possess and the similar vapour pressure of original refrigeration agent, thereby provide similar volume (Volumetric capacity, VC).But if substitute original refrigeration agent with simple material, because therefore its volume difference needs to change compressor or transform original condensed device or vaporizer greatly, and is difficult to obtain and original refrigeration agent similar performance coefficient.

One of can head it off be exactly to utilize mix refrigerant.The characteristic of mix refrigerant is help to cooperate when making the coefficient of performance (COP) be similar to original refrigeration agent, and possessing with the similar volume of original refrigeration agent (VC) does not need to transform greatly compressor.If possess this condition, producer does not need to consume compressor replacement charge and extra charge.

When mix refrigerant takes place to evaporate or is condensing at isopiestic state, vaporization temperature or condensing temperature keep certain azeotropic refrigerant (Azeotropes) as pure refrigeration agent, also have to take place evaporation can rise with regard to vaporization temperature and take place the condensing mixed non-azeotropic refrigerant that can reduce with regard to condensing temperature (Non Azeotropic Refrigerant Mixtures, NARMs).The characteristic of mixed non-azeotropic refrigerant refers to ' temperature glide phenomenon ' (Gliding Temperature Phenomenon) like this, the temperature difference between evaporation starting point and the end point is ' it is poor that temperature is glided ' (GlidingTemperature Difference, GTD), above-mentioned GTD is according to kind and the composition of the pure substance of forming mix refrigerant, and its GTD value changes greatly.

Therefore in nearest non-azeotropic (the Non Azeotropic Refrigerant Mixtures) mix refrigerant exploitation GTD less than 3 ℃ near azeotropic mixed refrigerant (Near AzeotropicRefrigerant Mixtures) after, more frequent as attempting of using of refrigeration agent, the mix refrigerant of many types has been proposed as the surrogate of CFC and HFC and HCFC in the past few years.It is moiety that but several materials have comprised the HCFC that Montreal Protocol bans use of, and therefore long-term viewpoint is not suitable for substitute materials.

Du pont company has not been developed damage the ozone layer (ODP=0) so far, and (GWP=1,430) HFC that the index that warms is lower is used for automobile and refrigerator, but this can not become long-term substitute materials, is also classified as the restriction object by the capital of a country letter of agreement.Nearest Dupont has been developed the product that is HFO-1234yf and has been promoted with high price, and this product also is flammable product, but can be used as automobile or refrigerator refrigeration agent.

And the HFC that is banned use of by the capital of a country letter of agreement forms, the long-term unaccommodated surrogate of viewpoint.Also have development and sale such as company of U.S. a company (AllaidSignal Inc.) the binary mix refrigerant (50 weight %R32/50 weight %R125) of R-410A, exceed 60% and the pressure height that must transform compressor and system causes Material Strength for condensed device also to need the problem that improves but this refrigeration agent exists the original HCFC of its steaming pressure ratio.

Analyze in the patent of the novel mixed component of alternative R-134a of recent Korea S invention, as follows to the characteristic of the influence (GWP) of greenhouse effects of the earth and temperature head (GTD):

On Korea S's domestic (following identical) stating Patent communique herd number 10-0405189 number, methylene fluoride (CH2F2, below ' HFC-32 '), 1,1,1,2-Tetrafluoroethane (CH2FCF3, below ' HFC-134a ') and 1,1,1,2,3,3,3-heptafluoro-propane (CF3CHFCF3, below ' HFC-227ea ') mixture on mix Trimethylmethane (CH (CH3) 2CH3, below ' R-600a '), 1,1,1,2,3,3-HFC-236fa (CHF2CHFCF3, below ' HFC-236ea ') and butane (C4H10, below ' R-600 ') in the composition or the HFC-32 that select, 1,1-C2H4F2 C2H4F2 (CH3CHF2, below ' HFC-152a ') and the mixture of HFC-227ea on mix R-600a, select the quaternary mixed refrigerant constituent behind the composition among HFC-236ea and the R-600, use as the alternative refrigerant of the difluorochloromethane that uses so far (CHClF2: following ' HCFC-22 '), do not damage the ozone layer, putting down in writing the mix refrigerant constituent that can use to the refrigeration agent material of household refrigerator and automative air conditioning etc.

Contain that (CH3F2 is the 1st composition HFC-32), with 1 with methylene fluoride disclosing for 10-305080 number with the communique herd number, (CH3CF3 HFC-143a) is the 2nd composition to 1,1-Halothane, by cyclopropane (C3H6, RC-270), 1,1,1,2,3,3,3-heptafluoro-propane (CF3CHFCF3, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH3CF2CF3, HFC-245cb), 1,1,1,2,3, the 3-HFC-236fa (CHF2CHFCF3, HFC-236ea), butane (C4H10, R-600), and the tetrafluoro ethyl difluoro methyl ether (CHF2OCHF2, HFE-134) and five fluorine methyl ethyl ether (CF3CF2OCH3, HFE-245) form a refrigerant mixture that composition is the HCFC-22 of the 3rd composition of selecting among the group

Putting down in writing for 10-400345 number with the communique herd number by methylene fluoride (CH2F2, following HFC-32) and 1,1,1-Halothane (CH3CF3, following HFC-143a) and 1,1-C2H4F2 C2H4F2 (CH3CHF2, following HFC-152a) and 1,1,1,2,3,3,3-heptafluoro-propane (CF3CHFCF3, following HFC-227ea), Trimethylmethane (CH (CH3) 2CH3, R-600a), 1,1,1,2,3,3-HFC-236fa (CHF2CHFCF3, following HFC-236ea) and butane (C4H10, following R-600) the refrigeration agent constituent of a compound of selecting among the composition group

Contain with methylene fluoride (CH 3F 2 having put down in writing for 10-305905 number with the communique herd number, HFC-32) be the 1st composition, contain perfluoropropane (C 3 F8 as the 2nd composition and the 3rd composition, PFC-218) and 1,1-C2H4F2 C2H4F2 (CH 3 CHF 2, HFC-152a) or cyclopropane (C 3H 6, RC-270) and 1,1,1,2, the 2-pentafluoropropane (CH 3 CF 2 CF 3, HFC-245cb) or butane (C 4 H 10, R-600) and tetrafluoro ethyl difluoro methyl ether (CHF 2 OCHF 2, HFE-134) HCFC-22 substitutes the constituent with refrigeration agent

Disclose for 10-0333503 number with the communique herd number the 1st composition that contains be methylene fluoride (CH 3 F 2, HFC-32), the 2nd composition is 1,1,1-Halothane (CH 3 CF 3, HFC-143a), by cyclopropane (C 3 H 6, RC-270), 1,1,1,2,3,3,3-heptafluoro-propane (CF 3 CHFCF 3, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH 3 CF 2 CF 3, HFC-245cb), 1,1,1,2,3, the 3-HFC-236fa (CHF 2 CHFCF 3, HFC-236ea), butane (C 4 H 10, R-600), and the tetrafluoro ethyl difluoro methyl ether (CHF 2 OCHF 2, HFE-134) and five fluorine methyl ethyl ethers (CF 3 CF 2 OCH 3, HFE-245) form a refrigerant mixture that composition is the HCFC-22 of the 3rd composition of selecting among the group

Putting down in writing as R-22 alternative refrigerant for 10-0682828 number with the communique herd number, by methylene fluoride (CH2 F2, below ' HFC-32 '), 1,1,1, the 2-Tetrafluoroethane (CH2FCF3, below ' HFC-134a '), CF3I (CF3I, below " 13I1) difluorochloromethane of forming substitutes the constituent of (ternary) azeotropy mix refrigerant

Putting down in writing about selecting the combination propylene 1,1,1,2-Tetrafluoroethane, 1,1-C2H4F2 C2H4F2, the mix refrigerant of forming behind dme and the Trimethylmethane and use the refrigeration system of this refrigeration agent for 10-0492172 number with the communique herd number.Mix refrigerant according to good example of the present invention discloses R-1270 (propylene) 30 and the 70 weight portions contained, R-134a (1,1,1,2-Tetrafluoroethane) 1 and 69 weight portions, and the refrigerant mixture of R-152a (1,1-C2H4F2 C2H4F2) 1 and 69 weight portions,

Methylene fluoride (CH2F2 is disclosed on the open number of domestic stating Patent communique 10-2005-0057852 number, following HFC-32) and | 1,1,1-Halothane (CH3CF3, following HFC-143a) and cyclopropane (C3H6, following RC-270) or the component of the refrigeration agent formed of a compound of selecting in the propane (C3H8, following R-290).

But the mix refrigerant constituent in the above-mentioned patent has more than 5～7 degree because of the temperature head in the vaporizer (GTD), can reduce cooling performance, and each warmization index ' HFC-32 ' is 675, ' HFC-134a ' is 1,430, ' HFC-227ea ' is 3,320, ' HFC-236ea ' is 9,810, ' HFC-152a ' is that 124 material and warmization index are minimum, index is that 3 R-600 or any material among the R-600a mix, and can't make also that to meet the GWP that reaches an agreement in the whole world be refrigeration agent below 150.Therefore, the refrigeration agent of this type of patent also belongs to limited object.

R-1270 (propylene) 1 and 99 weight portions by freezing/idle call mix refrigerant are disclosed on Korea S's domestic (following identical) communique herd number 10-0492169 number, below R-290 (propane) the 98 weight portions, R134a (1,1,1, the 2-Tetrafluoroethane) mix refrigerant of 1 and 70 weight portions composition

Used by R-134a (1,1,1 having recorded and narrated for 10-0540286 number with the communique herd number, the 2-Tetrafluoroethane) 1 and 78 weight %, RE-170 (dme) 1 and 78 weight %, the refrigeration system of the mix refrigerant that R-600a (Trimethylmethane) 21 and 98 weight % form

At the methylene fluoride of having put down in writing for 10-0571358 number with the communique herd number by methane series refrigeration agent composition (CH2F2, following R-32)

Propane (CH3CH2CH3, following R-290), propylene (CH3CH=CH2, following R-1270) mix to form, its ratio of components is whole 100 weight % to be mixed the characteristics of consisting of and become low temperature with substituting mix refrigerant with the methylene fluoride of methane series refrigeration agent composition (CH2F2) 5～40 weight % and propane (CH3CH2CH3) 35～70 weight % and propylene (CH3CH=CH2) 25～60 weight %.

On the composition that discloses the refrigerant mixture that can substitute the HCFC-22 use with communique herd number 10-0305079, comprise with methylene fluoride (CH2F2, HFC-32) 40 and 96 weight % are the 1st composition, its the 2nd composition and the 3rd composition are by cyclopropane (C3F6, RC-270) and 1,1,1,2, the 2-pentafluoropropane (CH3CF2CF2, HFC-245cb) and butane (C4 H10, R-600) and tetrafluoro ethyl difluoro methyl ether (CHF2OCHF2, HFE-134) form select among the group after, each fluorine cpd that comprise with 1 and 40 weight % and 4 and 40 weight % is the content of the mixture of refrigeration agent.

Putting down in writing for 10-0540284 number with the communique herd number about selecting combination propane, 1,1,1,2-Tetrafluoroethane, the mix refrigerant of forming behind dme (following DME) and the Trimethylmethane and the refrigeration system that utilizes this refrigeration agent.Disclose according to the mix refrigerant of good example of the present invention and to have contained R-290 (propane) 30 and 98 weight %, R-134a (1,1,1,2-Tetrafluoroethane), 1 and 70 weight %, the refrigerant mixture of RE-170 (dme) 1 and 70 weight %,

Putting down in writing about selecting the combination propylene 1,1,1,2-Tetrafluoroethane, 1,1-C2H4F2 C2H4F2, the mix refrigerant of forming behind dme and the Trimethylmethane and utilize the refrigeration system of this refrigeration agent for 10-540280 number with the communique herd number.R134A (1,1,1,2-Tetrafluoroethane) 1 and 69 weight %, the refrigeration agent constituent that R-152a (1,1-C2H4F2 C2H4F2) 1 and 69 weight % form have been put down in writing by R-1270 (propylene) 30 and 70 weight % according to the mix refrigerant of good example of the present invention.

Refrigeration agent greenhouse effects of the earth index in this type of patent of invention is lower, but temperature head (GTD) is 5～7 degree, freezes on the vaporizer, reduces cooling performance greatly.And provide similar volume (Volumetric capacity, VC), but because being non-azeotropic refrigerant, compressor be must change or original condensed device or vaporizer transformed greatly, in addition be difficult to obtain and original refrigeration agent similar performance coefficient, so there is the problem points that to revise system inevitably.

Summary of the invention:

The purpose of this invention is to provide a kind of Global warming index value (GWP) 1,1,1,2-Tetrafluoroethane (HFC-134a) that substitutes lower, good energy-conserving effect and use the novel environment-friendly refrigerant constituent.

Technical scheme of the present invention: a kind of alternative 1,1,1,2-Tetrafluoroethane (HFC-134a) is used the novel environment-friendly refrigerant constituent, the moiety of mix refrigerant is propane (R-290) 50-56kg of hydrocarbon system, Trimethylmethane (R-600a) 40-49kg is the basis, adds normal butane (R-600) 2-5kg and propylene (R-1270) 1-3kg, adds hexamethyl silicone oil additive 0.5-1kg and accomplishes near azeotropic mixed refrigerant.

For reaching the appeal purpose, the present invention mixes each moiety, accomplished nearly azeotropic material, its depletion of the ozone layer index (ODP) is 0, and global warming potential (GWP) is 3 near azeotropic mixed refrigerant (Near Azeotropic Refrigerant Mixtures).

According to the mix refrigerant constituent of the present invention of above-mentioned composition and use the refrigeration system of this constituent

1) because the depletion of the ozone layer index of composition mix refrigerant material is 0.0, when the refrigeration agent omission taking place or discarding the refrigeration agent constituent, prevents that the effect of global depletion of the ozone layer is more obvious

2) can be reduced to (GWP) lower than the global warming potential of original R-12 (10,890) R-134a (1,430).

3) the mix refrigerant constituent according to the present invention mix refrigerant that is nearly azeotropic, the variation that can not form along with phase change is so use pure refrigeration agent equally can stablize the use refrigeration system.

The change of refrigerating effect also can not take place in the composition separation phenomenon when 4) omitting the refrigeration agent constituent, during as if omission, only needs to fill and can use.

5) use mix refrigerant constituent of the present invention can improve thermo-efficiency freezing, air-conditioning, also have and original lubricating oil PAG oil between interchangeability.

6) use refrigeration agent constituent of the present invention to improve refrigerating effect more than 5～10%, its energy-saving effect is fine.

' refrigeration agent constituent ' of the present invention means the combination of two or more different refrigeration agents, also comprises refrigeration agent constituent additive accompanying information in addition.

Because boiling point (BoilingPoint) difference between the refrigeration agent of general refrigeration agent constituent, can not mix and cause disconnected from each other and the occurrence temperature slope, develop this temperature ramp being minimum 1 ℃ is very difficult with interior nearly azeotropy mix refrigerant constituent.

In the present invention, in order to solve the problem of temperature ramp, thereby the inventor can obtain the nearly azeotropy mix refrigerant constituent that minimizes the said temperature slope by adding hexamethyl silicone oil on the mix refrigerant of selecting combination.

Because mix refrigerant constituent of the present invention is that depletion of the ozone layer index (ODP) is 0.0, during evaporation temperature ramp be 1 ℃ with interior nearly azeotropy mix refrigerant constituent, can use as original pure refrigeration agent.Also have the value near the coefficient of performance (COP) and the volume (VC) of R-12 or R-134a, so do not need to change any part of refrigeration system, can substitute refrigeration agents such as the R-12 of existing use or R-134a.

Substitute the mix refrigerant constituent in order to develop nearly azeotropy according to the present invention, the inventor has used the CYCLE-D program of United States of American Standards Institute (the National Institute ofStandards and Technology) exploitation of being responsible for freezing/heat pump performance.By program, the factor of/air-conditioning freezing to form is example, has explained the thermodynamics of heat exchanger and compressor etc. and heat passage, has finally used all combinations.One of important factor of the accuracy of determination procedure is exactly the physics value of refrigeration agent constituent.Utilized in the U.S. in this program, the Ghana Chinese Stalin-big (name: Carnahan-Starling-De Santis of standard is done by Japan; CSD) refrigerant condition equation, multiple refrigeration agent has been calculated the dew point (Dew Point) of the bubble point (Bubble Point) that generates bubble and gas condensing back generation after, done the temperature ramp line chart of nearly azeotropy ternary refrigerant constituent.CSD refrigerant condition equation is in United States of American Standards Institute (NationalInstitute of Standards and Technology) exploitation, and the whole world that its accuracy and suitability have been verified is freezing/the widely used program of enterprise, institute, university that air-conditioning is relevant.For exploitation and the implementation of doing the mix refrigerant constituent, use real data to be the input data as far as possible.

The inventor judge the depletion of the ozone layer index (ODP) of alternative refrigerant constituent must 0.0 and global warming potential (GWP) to try one's best lower, so utilize said procedure, for the mix refrigerant constituent of doing nearly azeotropic added additive hexamethyl silicone oil in the mixture that propane (R-290) and Trimethylmethane (R-600a) are formed after, developed the mix refrigerant constituent.

That is, do not worry damaging the ozone layer, temperature ramp (TG) is in 1 ℃, and its global warming potential (GWP) is 3 nearly azeotropy mix refrigerant constituent.

When the present invention replaces for the freonll-11 series coolant R-12 of automative air conditioning and refrigerator or R-134a, there is not change reason refrigeration system, only adjust the operable environmental protection refrigerant constituent of refrigerant amount, propane (R-290) 50～56kg and Trimethylmethane (R-600a) 40～49kg based on hydrocarbon system, add normal butane (R-600) 2～5kg and propylene (R-1270) 1～3kg, behind additive-hexamethyl silicone oil of being nearly azeotropic interpolation 0.5～1kg, the depletion of the ozone layer index is called (ODP=0), and its global warming potential is (GWP=3) mix refrigerant.

Fig. 1 in the accompanying drawing describes the near azeotropic mixed refrigerant constituent along with good embodiment of the present invention in detail below.

Description of drawings

The common air-conditioning machine block diagram that Fig. 1 the present invention uses

The temperature ramp line chart of the binary mix refrigerant constituent that Fig. 2 obtains by REFPROP8.0 program of the present invention

Fig. 3 is by the minimized pressure-enthalpy of refrigeration agent constituent of the present invention (P-h) line chart

Pressure-enthalpy of Fig. 4 R-134a (P-h) line chart

Pressure-enthalpy (P-h) line chart of Fig. 5 " R-436A "

Pressure-enthalpy (P-h) line chart of Fig. 6 " SC-134A1 "

Liquid and the gas composition separating experiment of Fig. 7 " R-436A " the 1st top condition refrigeration agent

Liquid and the gas composition separating experiment of Fig. 8 " SC-134A1 " the 2nd top condition refrigeration agent

Fig. 9 forms with the best of " R-436A " the 1st top condition refrigeration agent and filled 60% o'clock, at-18.28 ℃ of composition separating experiments that leakages take place figure as a result

Figure 10 filled 60% o'clock with " SC-134A1 " the 2nd top condition refrigeration agent best the composition, at-18.28 ℃ of composition separating experiments that leakages take place figure as a result

Figure 11 forms filling 15% o'clock with the best of " R-436A " the 1st top condition refrigeration agent ,-18.28 ℃ of composition separating experiment results that leakages take place

Figure 12 forms 15% o'clock composition separating experiment result-18.28 ℃ of generation leakages of filling with the best of " SC-134A1 " the 2nd top condition refrigeration agent

The freezing performance that Figure 13 R-12, R-134a and " R-436A " reach " SC-134A1 " alternative refrigerant compares.

Figure 14 is 7 degrees centigrade in vaporizer inner refrigerant temperature, and condensed device inner refrigerant temperature is under 45 degrees centigrade the test conditions, additive performance and temperature head (GTD) experimental result table.

The global warmization index (GWP) of refrigeration agent constituent among Figure 15 the present invention.

Flammable the rolling off the production line of minimum explosion (LFL) comparison sheet of refrigeration agent constituent among Figure 16 the present invention.

Embodiment:

Embodiment 1

Present embodiment is the 1st top condition:

Mix propane (R-290) 54kg, behind Trimethylmethane (R-600a) 45.9kg, in order to do the near azeotropic mixed refrigerant constituent, added hexamethyl silicone oil 0.1kg with additive and made the refrigeration agent constituent.

Embodiment 2

Present embodiment is the 2nd top condition:

Mix propane (R-290) 53kg, behind Trimethylmethane (R-600a) 43.9kg, add normal butane (R-600) 2kg and propylene (R-1270) 1kg, in order to do the near azeotropic mixed refrigerant constituent, add 0.1kg hexamethyl silicone oil additive and made the refrigeration agent constituent.

Experimental example 1 (theory and the test of actual temperature slope)

Fig. 2 represents the temperature ramp line chart of the binary mix refrigerant constituent that does not add additive that obtains by REFPROP8.0 program of the present invention.But in order to form the near-azeotrope refrigerant constituent of purpose of the present invention, added additive after, thereby can learn as its temperature ramp of Fig. 3 result as the testing apparatus of test chart 1 and to minimize.

Experimental example 2 (composition separating experiment)

Whether nearly azeotropic has carried out the composition separating experiment in order to confirm refrigeration agent constituent of the present invention.

The best filling of the present invention consists of:

1) (R-290) 54kg/ (R-600a) 45.9kg/ (additive) 0.1kg (following " R-436A "

2) (R-290) 53kg/ (R-600a) 43.9kg/ (R-600) 2kg/ (R-1270) 1kg/ (additive) 0.1kg. (following " SC-134A1 ")

For carrying out the separation test that above-mentioned top condition is formed, utilize chromatographic instrument (Gas Chromatograph) analysis, obtained as Fig. 7, Fig. 8 result displayed, learn in liquids and gases and also mix with identical proportion of composing.

In order more clearly to form separating experiment, the UL2182 standard-required at filling 60% liquid refrigerant in the container and filling 15% o'clock, is explained by forming to separate under several temperature condition, is determined the worst condition.Therefore refrigeration agent constituent of the present invention has carried out forming the separation explanation under following temperature condition.

Filled 60% o'clock :-18.28 ℃, 25.0 ℃, 54.4 ℃

Filled 15% o'clock :-18.28 ℃, 25.0 ℃, 60.0 ℃

Form at filling 60% and 15% o'clock separation test of filling for carrying out above-mentioned top condition, utilize chromatographic instrument (Gas Chromato graph) analysis, each result such as Fig. 9, Figure 10 of filling 60% o'clock represent, each result such as Figure 11, Figure 12 of filling 15% o'clock represent, learn that the proportion of composing that mixes is identical no matter be to fill 60% or 15% in liquids and gases.

Experimental example 3 (performance test)

Figure 13 compared refrigeration agent of the present invention " R-436A " reach " SC-134A1 " theoretical performance and and R-12R-134a between performance relatively.

Remarks: REF.APL.Con.:Means Low Back Pressure Conditions

Condensed device temperature: 40.0 ℃

Evaporator temperature :-30.0 ℃

Sub cooled fluid temperature: 30.0 ℃

Superheated gas temperature: 30.0 ℃

United States of American Standards Institute PEFPROP 8.0 (Based on NIST, PEFPROP 8.0 ﹠amp; NewDeveloped Refrigerant Program) redaction of specially adding by (strain) TechnoChem has been carried out Theoretical Calculation.

* COP: the coefficient of performance (Coefficient of performance, the thing that applies on total refrigerating effect/compressor)

*GWP：3

R-12, the R-134a refrigeration agent is widely used in houshold refrigerator and automative air conditioning, but is limited at present to use and carries out the exploitation of alternative refrigerant.Refrigeration agent will consider not only to the influence of global environment that the influence of refrigeration agent itself also will be considered start-up system and the influence of the carbonic acid gas that takes place during the electric power that uses, uses index (the TEWI:total equivalentwarming impact) expression of warming of total equivalence this moment.Direct influence according to this index family air-conditioning quilt refrigeration agent is 4%, and remote effect are 96%, and air-conditioner efficiency is very important on the link of selection refrigeration agent.

But the pure refrigeration agent than R-134a excellent in performance in freonll-11 series does not also have exploitation.Following thermomechanical property relatively goes up, and evaporator temperature is made as 0 ℃, and the temperature of condensed device is made as 40 ℃, and being made as in the outlet of evaporator outlet and condensed device does not have temperature of superheat and supercooling temperature, and the compressor gangway is made as isoentropic process.

At Fig. 4 (R-134a), Fig. 5 (" R-436A "), Fig. 6 (" SC-134A1 ") " pressure-enthalpy line chart of representing each refrigeration agent.

By Figure 13, original R-12 and its coefficient of performance of R-134a (COP) of HFC series refrigeration agent are lower than " R-436A " and " SC-134A1 ", have only the efficient of " R-436A " and " SC-134A1 " to be higher than R-12, R-134a10%.

Be as the criterion with TEWI (all equivalences warm index), performance is more important than the influence of refrigeration agent itself, and therefore refrigeration agent " R-436A " is the most suitable with " SC-134A1 " as an alternative.And the pressure ratio of two refrigeration agent constituents or the compressor temperature that spues is also very approaching.So " R-436A " and " SC-134A1 " do not have depletion of the ozone layer index (ODP), its GWP is low-down 3, is used in R-12 on long terms, and the alternative refrigerant of R-134a is also out of question.

(be 7 degrees centigrade in vaporizer inner refrigerant temperature, condensed device inner refrigerant temperature is under 45 degrees centigrade the test conditions to experimental example 4, the experimental result of additive performance and temperature head (GTD).) as Figure 14, to add the additive experiment under the different moietys, as a result among the figure embodiment 1,2 shown peak performance coefficient (COP) although 12.9% and 13.3%. particularly be mix refrigerant, comparative example 1,2 shows when not having additive such as among the figure, its temperature head (GTD) reaches 5.0～5.3 degrees centigrade, but show that as embodiment 1,2 results the evaporator temperature difference has only 0.1 degree when adding additive, shows it is near-azeotrope refrigerant.Therefore learn, additive be make in the near-azeotrope refrigerant indispensable.※ COPr: the freezing coefficient of performance (Coefficient of performance)

QE: vaporizer (cold cut) capacity (Evaporator capacity)

Tdis: the compressor temperature (Compressor discharge temperature) that spues

COPr _Diff: the freezing coefficient of performance of comparing with R-134a is poor

QE _Diff: the vaporizer of comparing with R-134a (cold cut) capacity difference

Tdis _Diff: the compressor of comparing with the R-134a temperature head that spues

GTD: the vaporizer of comparing with R-134a is gone into, temperature out poor (GlideTemperature Difference)

Experimental example 5 (the global warmization index (GWP) of refrigeration agent constituent among the present invention)

As Figure 15, shown that according to different moietys global warming potential refers to, the global warming potential of hydrocarbon serial refrigeration agent refers to all very low.

Experimental example 6 (flammable the rolling off the production line of minimum explosion (LFL) of refrigeration agent constituent among the present invention)

As Figure 16, (the experiment specification: ASTM-E-6812008), in the moiety that adds additive, combustibility has been guaranteed average security more than 50% to do flammability test under the different moietys.

Claims (1)

1. substitute 1,1,2-Tetrafluoroethane environmental protection refrigerant constituent, it is characterized in that: the moiety of mix refrigerant is propane (R-290) 50-56kg of hydrocarbon system, Trimethylmethane (R-600a) 40-49kg is the basis, add normal butane (R-600) 2-5kg and propylene (R-1270) 1-3kg, add hexamethyl silicone oil additive 0.5-1kg and accomplish near azeotropic mixed refrigerant.

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