WO2011038570A1

WO2011038570A1 - Refrigerant composition

Info

Publication number: WO2011038570A1
Application number: PCT/CN2010/001465
Authority: WO
Inventors: 王鑫; 庞峰; 孙森; 胡金正
Original assignee: 山东东岳化工有限公司
Priority date: 2009-09-29
Filing date: 2010-09-21
Publication date: 2011-04-07
Also published as: CN101671542A

Abstract

A refrigerant applied to automobile air conditioners for replacing HFC-134a. The refrigerant comprises 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroethane (HFC-152a), or can further comprise isobutane (HC-600a). The preparation method of the refrigerant comprises physically mixing the above components according to the corresponding mixture ratio under liquid phase. The refrigerant has equivalent physical properties to those of HFC-134a, is compatible with pipelines and components of the prior systems for HFC-134a, has safe use, higher refrigeration efficiency and quite low temperature glide, is free from damaging atmospheric ozone layer and has quite low GPW value and reduces replacement fee. The refrigerant can be used as a replaced refrigerant of HFC-134a in automobile air conditioners.

Description

Refrigerant composition technical field

The present invention relates to the field of refrigerants, and relates to a refrigerant composition, and more particularly to a refrigerant composition for use in an automotive air conditioning system instead of 1,1,1,2-tetrafluoroethane (HFC-134a). Background technique

1,1,1,2-tetrafluoroethane (HFC-134a) is widely used in automotive air conditioners and other refrigeration systems, but its greenhouse effect potential (GWP value) is higher, 1430 times that of C0 ₂ Moreover, the operating conditions of automobile air conditioners are complex and changeable, and the amount of refrigerant leakage is large, which contributes a lot to global warming. Auto air conditioners have thus become one of the first refrigeration and air conditioning equipments to disable high GWP refrigerants. . According to the requirements of the F-gas control regulations adopted by the European Union: From January 1, 2011, the EU will ban new-produced automotive air conditioners from using refrigerants with a GWP greater than 150; in January 2011 During the six years from the 1st to the 1st of January 2017, the refrigerants with a GWP value greater than 150 will be phased out in the use of automotive air conditioners; from January 1, 2017, all automotive air conditioners will be banned from using GWP values greater than 150. Refrigerants. Therefore, the use of low-GWP refrigerants in the refrigeration and air-conditioning industry (especially automotive air-conditioning) has become a trend and inevitable, and research and development work on alternatives is extremely urgent.

At present, the international research direction of HFC-134a replacement in automotive air conditioners is mainly carbon dioxide (C0 ₂ ), 1,1-difluoroacetamidine (HFC-152a), 2,3,3,3-tetrafluoropropene (HFO). -1234yf) and some mixed working solutions, but each has its own advantages and disadvantages, is still not ideal, and does not form a clear alternative direction. Among them, the use of co ₂ greenhouse effect potential is low, non-flammable, but it needs to redesign and optimize the system, high cost, high system pressure, low energy efficiency; less use of 1,1-difluoroethane (HFC-152a) system High energy efficiency and low refrigerant cost, but its flammability is strong, the secondary circuit system is required, and the compressor discharge temperature is high; the 2,3,3,3-tetrafluoropropene (HFO-1234yf) system is less modified. The flammability is weak and the compressor discharge temperature is low, but its energy efficiency is low, the refrigeration capacity is small, and the refrigerant cost is high. In addition, when choosing a mixed working solution, in addition to comprehensive consideration of environmental protection, physical properties, energy efficiency, cost and other factors, due to the large leakage of automotive air conditioning refrigerant, in order to facilitate maintenance and maintenance, the slip temperature of the mixture is required to be as small as possible. .

Among the existing mixed working medium replacement technologies, patent applications US20080026977 and CN200780035213.6 disclose a mixture of tetrafluoropropene and heptafluorobutene, but the sliding temperature is relatively high and the cost is high: Patent application US20080308763, US7524805 and CN200580022108. X discloses HFO-1234ze and a binary or multi-component mixture selected from the group consisting of HFC-152a, HFC-227ea, HFC-134a, HFC-125, but if it is used to replace HFC-134a, it has lower energy efficiency and lower cooling capacity. Small, or high GWP, or large slip temperature; patent application US20080075673 discloses a mixture of HFO-1234ze and hydrocarbon composition, but its sliding temperature is larger and flammability is stronger: Patent application US20060022166 and CN200580019019. X Jian well mixtures of HFO-1234yf and HFO-1225yeZ composition, but the temperature is higher slip, high cost; patent applications US20060019857 and CN200580019197.2 disclose a mixture I consisting of _{HFO-1234ze. 3} and CF, but the CF The ODP value of ₃ I has not been determined to be zero recently, so the mixture still has some damage to the atmospheric ozone layer; patent applications US20060043331 and CN200580021136.X disclose HFO-12 A mixture of 34ze and C0 ₂ , but if used to replace HFC-134a, the pressure is higher and the slip temperature is higher.

In addition, patent application CN200610049650.0 discloses a mixture of HFC-161 and HFC-152a; Application CN200610052120.1 discloses a HFC-161, HFC- 152a or HC-600a and HC-600 and other components of the mixture; patent applications US20060116310 and US20060025322 discloses mixtures of HFC-152a and CF ₃ I thereof; Patent Application Publication CN200510119566.7 A mixture of CF ₃ I, HC-600 and HC-600a; patent application US2003178597 discloses a mixture of HC-600a, HFC-152a and CO ₂ : Patent application JP 11199863 discloses CF ₃ I, HC-600, HC- A mixture of 600a and HFC-152a; Patent Application CN98101170.5 discloses a mixture of HFC-152a, HC-600 and HC-600a; Patent Application WO 9529210 discloses a mixture of HFC-152a and HC-600a. These mixtures have lower GWP values than HFC-134a, but these mixtures have or have strong flammability, or have large slip temperatures, or are not compatible with existing automotive air conditioning systems, or are efficient. Lower, or expensive. Summary of the invention

The present invention aims to study the use of a refrigerant for replacing an HFC-134a in an automotive air conditioning system, so that the newly developed refrigerant substitute has the same physical properties as HFC-134a and the pipeline of the existing HFC-134a system. It is compatible with components, safe to use, and has high cooling efficiency, and it does not damage the atmospheric ozone layer. The GWP value is as low as possible and has a very small slip temperature.

The refrigerant composition of the present invention replacing HFC-134a is composed of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroacetamidine (HFC-152a), wherein each component As follows, are all mass percentages:

2,3,3,3-tetrafluoropropene: 50~95%

1,1-difluoroethane: 50~5 ^ο / _ο .

Preferably, the refrigerant composition of the present invention which replaces HFC-134a has the following composition, all of which are mass percentages:

2,3,3,3-tetrafluoropropene: 60~90%

1,1-difluoroacetamidine: 40~10%.

Moreover, the refrigerant composition of the present invention which replaces HFC-134a includes, in addition to 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroacetamidine (HFC-152a), It also contains isobutyl hydrazine (HC-600a), in which the components are as follows, all of which are mass percentages:

2,3,3,3-tetrafluoropropene: 50~90%

1,1-difluoroacetamidine: 5~48%

Isobutyl hydrazine: 2~5 /. .

2,3,3,3-tetrafluoropropene (HFO-1234yf) in the above composition, the molecular formula is CH ₂ CFCF ₃ , the molar mass is 114.04 g/mol, the normal boiling point is -29.35 ° C, and the critical temperature is 94.7. . C, the critical pressure is 3.375 MPa.

1,1-difluoroacetamidine (HFC-152a), its molecular formula is CHF ₂ CH ₃ , the molar mass is 66.05g/mol, the normal boiling point is -24.0'C, the critical temperature is 113.3 °C, and the critical pressure is 4.52MPa. .

Isobutane (HC-600a) has a molecular formula of CH(CH ₃ ) ₃ , a molar mass of 58.12 g/mol, a normal boiling point of -11.7 ° C, a critical temperature of 134.7 ° C, and a critical pressure of 3.63 MPa.

The refrigerant composition provided by the present invention is prepared by using 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1J-difluoroethane (HFC-152a), or 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf), 1,1-difluoroethane (HFC-152a) and isobutane (HC-600a), which can be physically mixed in the liquid phase according to their corresponding ratios. .

The present invention has the following advantages and benefits:

a. Environmental performance Table 1 lists the environmental performance comparison between the present invention and HFC-134a. It can be seen that the ozone destruction potential (ODP) of the present invention is zero, does not damage the atmospheric ozone layer, and the greenhouse effect potential (GWP) is very low, less than 100, compared with HFC-134a, reducing the emission potential by more than 95%, meeting the current EU environmental protection requirements for automotive air conditioning refrigerants, and fully complying with the long-term environmental protection requirements of HFC-134a replacement.

Table 1 Comparison of environmental performance

b. Thermal parameters:

Table 2 lists the thermal parameters of the present invention compared to HFC-134a at an evaporation temperature of -1 Torr, a condensing temperature of 62 °C, and a superheat temperature of 10. C. Under the test conditions of 5°C overcooling and 80% compressor efficiency, the pressure of the refrigerant on the evaporator side is slightly higher than that of HFC-134a, and the pressure of the refrigerant on the condenser side is higher than that of HFC-134a. Slightly low, but very close to HFC-134a, which not only achieves a smaller compression ratio, reduces compressor power consumption, but also meets the pressure requirements of direct charge replacement; compressor discharge temperature is comparable to HFC-134a, non-destructive The long-term stable operation of the compressor; and, the sliding temperature of the present invention is very small, and can be considered as an azeotropic mixture, which not only enhances the heat exchange in the two devices, but also the composition of the mixture does not change when the leakage occurs. It is good for the maintenance and maintenance of car air conditioners.

Comparison of thermal parameters

C. Thermal performance

Table 3 lists the thermal performance of the present invention compared with HFC-134a. The COP value of the present invention is comparable to that of HFC-134a, which not only improves the energy efficiency of the replacement of HFC-134a by tetrafluoropropene, but also shows that some ratios are also exhibited. A certain energy-saving effect; volume cooling capacity is also equivalent to HFC-134a, which not only overcomes the shortage of low-temperature when tetrafluoropropene replaces HFC-134a, but also shows a larger cooling capacity.

Thermal performance comparison

d. Direct filling performance

Moreover, the metal compatibility, the plastic material and the elastic material in the original HFC-134a system are compatible with the material compatibility test in accordance with international standards, and it is not necessary to replace the HFC-134a in the transition process. Replacement system Ingredients and piping: In addition, the binary mixture of the present invention is compatible with the ester oil (POE) and the alcohol oil (PAG) used in the HFC-134a system, as verified by the lubricant compatibility test. The ternary mixture is not only It is compatible with ester oils (POE) and alcohol oils (PAG) and is compatible with lower-priced mineral oils (MO). Therefore, the present invention is not only compatible with the piping and components of the existing HFC-134a system, but also requires no replacement of piping components and lubricating oil, and it is also possible to replace the lubricating oil with a lower-priced mineral oil (MO), which will greatly Reduce the cost of transitions in the HFC-134a replacement process.

In summary, the present invention is equivalent to the physical properties of HFC-134a, compatible with the pipelines and components of the existing HFC-134a system, safe to use, has high refrigeration efficiency, very small slip temperature, and does not destroy. The atmospheric ozone layer and GWP are very low, meeting the current EU environmental requirements for refrigerants, and also meeting the long-term development requirements of HFC-134a replacement. It is an ideal substitute for HFC-134a in automotive air conditioners. Best way to implement the invention

In order to facilitate an understanding of the refrigerant and its advantages of the present invention, several specific examples are given below, wherein the proportions of the components are all by mass.

Example 1 : 50% by mass of 2,3,3,3-tetrafluoropropene and 50% by mass of 1,1-difluoroethane were physically mixed in a liquid phase to serve as a refrigerant.

Example 2: 60% by mass of 2,3,3,3-tetrafluoropropene and 40% by mass of 1, difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.

Example 3: A mass percentage of 75% of 2,3,3,3-tetrafluoropropene and 25% by mass of 1,1-difluoroethane were physically mixed in a liquid phase to serve as a refrigerant.

Example 4: 80% by mass of 2,3,3,3-tetrafluoropropene and 20% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.

Example 5: 90% by mass of 2,3,3,3-tetrafluoropropene and 10% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.

Example 6: 95% by mass of 2,3,3,3-tetrafluoropropene and 5% by mass of 1,1-difluoroacetic acid were physically mixed in a liquid phase to serve as a refrigerant.

EXAMPLES: 50% by mass of 2,3,3,3-tetrafluoropropene, 48% by mass of 1,1-difluoroethane, and 2% by weight of isobutyl hydrazine It is physically mixed as a refrigerant.

Example 8: 76% by mass of 2,3,3,3-tetrafluoropropene, 21% by mass of 1,1-difluoroethane and 3% by mass of isobutane in liquid phase It is physically mixed and used as a refrigerant.

Example 9: 90% by mass of 2,3,3,3-tetrafluoropropene, 5% by mass of 1,1-difluoroethane and 5% by mass of isobutyl hydrazine in liquid phase It is physically mixed and used as a refrigerant.

The environmental parameters of the refrigerant of the above embodiment are under the conditions of evaporating temperature of -1 'C, condensing temperature of 62'C, superheating temperature of 10'C, supercooling temperature of 5 °C, and compressor efficiency of 80%. The physical properties and thermal properties are listed in Table 4.

Remarks: * indicates the corresponding ratio to HFC-134a, where COP is the coefficient of performance. It can be seen from Table 4 that the ozone depletion potential (ODP) of the present invention is zero compared to the parameters and performance of the present invention, and the ozone depletion potential (ODP) is zero, and the greenhouse effect potential (GWP) is very low, less than 100.

The pressure of the evaporator-side refrigerant of the present invention is slightly higher than that of HFC-134a, and the pressure of the refrigerant on the condenser side is slightly lower than that of HFC-134a, but is very close to that of HFC-134a, so that not only less compression can be obtained. In comparison, the compressor consumes less work, and meets the pressure requirements of direct charge replacement: Moreover, the slip temperature of the present invention is very small, and can be considered as an azeotropic mixture, which not only enhances heat exchange in the two devices, but also occurs. The composition of the mixture at the time of leakage can be considered to be unchanged, which is beneficial to the maintenance and maintenance of the automobile air conditioner.

The COP value of the invention is equivalent to that of HFC-134a, which not only improves the energy efficiency of the replacement of HFC-134a by tetrafluoropropene, but also shows that certain ratios also show a certain energy saving effect; the volumetric refrigeration capacity is also equivalent to HFC-134a, which not only overcomes The shortage of low-temperature when tetrafluoropropene replaced HFC-134a, and some ratios also showed greater cooling capacity.

The present invention is compatible with metal materials, plastic materials, elastic materials, and the like in the original HFC-134a system: In addition, the binary mixture of the present invention and the ester oil (POE) and alcohol oil (PAG) used in the HFC-134a system. Compatible, the ternary mixture is compatible not only with ester oils (POE) and alcoholic oils (PAG), but also with lower-priced mineral oils (MO). Therefore, the present invention is compatible not only with the piping and components of the existing HFC-134a system, but also without replacing the piping components and lubricating oil, and also replacing the lubricating oil with a lower-priced mineral oil (MO). Will greatly reduce the cost of transition in the HFC-134a replacement process.

Claims

Claim

A refrigerant composition in place of HFC-134a, characterized in that the refrigerant contains two substances, 2,3,3,3-tetrafluoropropene and 1,1-difluoroacetic acid, the content of which is respectively For:

2,3,3,3-tetrafluoropropene: 50~95%

1,1-difluoroethane: 50~5 ^ο /ο

All are percentages by mass.

2. The refrigerant composition of claim 1 in place of HFC-134a, comprising:

2,3,3,3-tetrafluoropropene: 60~90%

1,1-difluoroethane: 40~10%

All are percentages by mass.

3. The refrigerant composition in place of HFC-134a according to claim 1, wherein the refrigerant further comprises isobutyl ruthenium, the component contents of which are:

2,3,3,3-tetrafluoropropene: 50~90%

1,1-difluoroacetamidine: 5~48°/ ₀

Isobutyl hydrazine: 2 to 5%

All are percentages by mass.

The method for preparing a refrigerant composition replacing HFC-134a according to claim 1 or 3, which comprises 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,1-difluoroethane. Alkane (HFC-152a), or 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1-difluoroacetamidine (HFC-152a) and isobutane (HC-600a), according to The corresponding ratio can be physically mixed in the liquid phase.