CN1070220C - Azeotropic mixture refrigerant used as substitut for freon 12 - Google Patents
Azeotropic mixture refrigerant used as substitut for freon 12 Download PDFInfo
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- CN1070220C CN1070220C CN 98101170 CN98101170A CN1070220C CN 1070220 C CN1070220 C CN 1070220C CN 98101170 CN98101170 CN 98101170 CN 98101170 A CN98101170 A CN 98101170A CN 1070220 C CN1070220 C CN 1070220C
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Abstract
The present invention relates to an azeotropic mixture refrigerant used as a substitute for freon 12. The azeotropic mixture refrigerant is prepared from 65% to 85% of difluoroethane, 11% to 29% of isobutane and 1% to 9% of butane. In the whole proportion range, an ozone depletion potential value ODP is zero, a global warming potential value GWP is approximately 110 and a phase change temperature drift parameter is small. In an optimal proportion, namely in the form of an azeotropic mixture, a normal boiling point is-29.0 DEG C and the azeotropic mixture refrigerant has no toxicity and high safety. The azeotropic mixture refrigerant of the present invention can be used as a direct-filling substitute for a refrigerator refrigerant CFC12 and has the advantages of low price, no need for replacing the existing CFC12 compressor and good economical and social benefits.
Description
The present invention relates to a kind of working medium of refrigerator, exactly, relate to a kind of refrigeration agent that is used for the azeotropic mixed working medium in replacement fluorine Lyons 12 (being Refrigerant 12).
The mankind are faced with the severeest since the dawn of human civilization ecocrisis; wherein very important a kind of phenomenon is exactly consume, the attenuation of ozonosphere; this variation of ozonosphere; will increase earth surface ultraviolet irradiation amount; might cause many planktonic organism death; influence aquatic ecosystem, the destruction of especially troubling is ozonosphere can be caused great harm to human health.And the loss day by day of the ozonosphere in the atmosphere mainly is because the long-term discharging and the accumulation of ozone depletion material (as freon-type material) causes.So, clear and definite regulation in the Montreal protocol, in the ozone depletion material, the Chlorofluorocarbons (CFCs) (CFCs) that comprises fluorine Lyons 12 endangers the most serious, belongs to absolute controlled and banned substance.
For many years, the scientific and technical personnel of countries in the world drop into the surrogate that Chlorofluorocarbons (CFCs) was sought and developed to a large amount of human and material resources.Because fluorine Lyons 12 (be Refrigerant 12, molecular formula: CF
2Cl
2, chemical code name: CFCl2, the refrigeration agent code name: R12) having good physics, chemical property, is suitable ideal refrigerator refrigerant, continued to use 60 so far surplus year, and still do not find the final surrogate of CFC12 so far.At present, the pure working substance substitute of the CFC alternative of using 12 mainly contains: HFC134a, HC600a, HFC152a etc., but the use of these pure working medium, must carry out scrap build to compressor and other refrigeration parts, that is to say that they can not substitute as the direct perfusion type of former CFC12 refrigeration system.Therefore, seek hot rerum natura and refrigeration performance and CFC12 and be close, can be used for the direct perfusion type alternate of CFC12 refrigeration system mixture refrigerant becomes the important selection scheme of people.Yet, although mixture refrigerant that develop both at home and abroad at present and on probation is a lot, but they all are zeotropes, as the MP39 of du pont company, THR01 of Tsing-Hua University or the like, these zeotrope refrigeration agents, all must just can reach the performance index of original CFC12 by suitable adjustment refrigeration system, therefore strictly speaking, they are not the direct perfusion type surrogate of CFC12.In addition, for zeotrope, when departing from specified proportioning, may cause the deterioration of performance of refrigerant systems as the mixture ratio that causes reality to fill because of controlling of production process is improper; And, the overwhelming majority all is based on HCFC22 configuration and forms in these mixing mediums, and according to the amendment of Montreal protocol, HCFC22 also is a controlled substance, some developed countries are advanced to 2000 with its disable period, and its final eliminating has been trend of the times.So the mixing medium that all that using at present contain HCFC22 also is cambic surrogate.
The purpose of this invention is to provide does not a kind ofly have model mixture refrigeration agent destruction, that can be used as the long-term surrogate of fluorine Lyons 12 refrigeration agents to atmospheric ozone layer.
Another purpose of the present invention provides performance, the energy-conservation again azeotropic mixture refrigerant of easy handling that a kind of direct perfusion type that can be used as fluorine Lyons 12 substituted, also can keep former refrigeration system.
The present invention is achieved in that it is a kind of mixture, and its moiety includes: C2H4F2 C2H4F2 (molecular formula: CHF
2CH
3, chemical code name: HFC152a, refrigeration agent code name: R152a), Trimethylmethane (molecular formula: C (CH
3)
3, chemical code name: HC600a, refrigeration agent code name: R600a) and butane (molecular formula: C
4H
10, chemical code name: HC600, refrigeration agent code name: R600); Its ratio range (weight percent) is: C2H4F2 C2H4F2 (HFC152a) is 65%～85%, and Trimethylmethane (HC600a) is 11%～29%, and butane (HC600) is 1%～9%.
A best proportioning of the present invention (weight percent) is: C2H4F2 C2H4F2 (HFC152a) is 75%, and Trimethylmethane (HC600a) is 20%, and butane (HC600) is 5%; At this moment, it is an azeotropic mixture.
The present invention is a kind of rather ideal " green " environment-friendly type refrigerator refrigerant, and the latent value ODP of its ozone depletion is zero, and life-time service can not produce destroying infection to the ozonosphere in the atmosphere; Its Global warming value GWP that dives is 110 (with CO
2Be 1, HFC134a is 1200), be far smaller than the correlation parameter of the refrigeration agent of HFC134a and above-mentioned other transition things, just very little to " Greenhouse effect " influence of global warming.The present invention has well near azeotropic characteristic in its claimed whole ratio range, but during best therein proportioning, then is azeotropic mixture, and the normal boiling point of this azeotropic mixture is-29.0 ℃.And in the temperature range of the whole cooling condition-35 of refrigerator ℃～+ 55 ℃, different proportioning embodiment of the present invention have very little transformation temperature slippage parameter (bubble dew-point temperature all＜1.5 ℃).Safe class of the present invention is A level (according to a U.S. ASHREA standard), and totally nontoxic is flammable.Corresponding to identical temperature of saturation, the saturation pressure of the present invention and CFC12 is very approaching, and refrigerating effect per unit swept volume and unit volume compression work are also all suitable with CFC12, and the theoretical value of its coefficient of performance COP also is better than CFC12.The present invention is because of containing alkane, employed mineral lubricating oils mixes fully in itself and the former CFC12 refrigeration system, so the direct perfusion type that the present invention can be used as refrigerator refrigerant CFC12 substitutes, promptly can be not oil change and directly apply to the CFC12 compressor of refrigeration system of refrigerator more.In fact the present invention's refrigeration agent of can be used for all CFC12 refrigerating appliances substitutes.
As the long-term surrogate of CFC12, the present invention compares with Trimethylmethane with pure refrigeration agent HFC134a, except himself price is lower, has outside the refrigeration agent of the reduction cost advantage; As when using HFC134a and Trimethylmethane CFC alternative 12, all must redesign each parts of refrigeration system that comprise compressor; And use CFC alternative 12 of the present invention, just need not change the compressor this point and just can obtain extremely considerable great economic benefit.As everyone knows, the CFC12 compressor production line of China mostly is that the eighties～the nineties introduces, and only compressor for refrigeration has just had more than 1,000 ten thousand throughput.If use above-mentioned pure working medium HFC134a or Trimethylmethane to come replacement fluorine Lyons 12, above-mentioned production line will become the scrap iron a pile; At domestic As-Is, will introduce new compressor production line again, perhaps whole imported compressors, this not only can cause the huge waste of state-owned assets and foreign exchange, and increases production cost greatly.For example, the R134a of a 125W or R600a imported compressor need 600 yuan of Renminbi approximately, and the R12 compressor of a homemade 125W only needs 350 yuan of Renminbi.In addition,, the operation of the refrigeration system that the present invention constitutes as azeotropic mixture refrigerant and operation are basic identical when using pure refrigeration agent CFC12, and it is fairly simple easy to operate, but save energy also.
Below in conjunction with accompanying drawing, further specifically introduce composition of the present invention and characteristics.
Fig. 1 is the curve comparison diagram of temperature of saturation-saturation pressure of the present invention and CFC12.
Fig. 2 is the comparison synoptic diagram of the performance perameter COP of two compressors difference trial edition inventions and CFC12.
The present invention is a kind of hybrid refrigeration working medium, and its moiety includes: C2H4F2 C2H4F2 (molecular formula: CHF
2CH
3, chemical code name: HFC152a, refrigeration agent code name: R152a), Trimethylmethane (molecular formula: C (CH3) 3, chemical code name: HC600a, refrigeration agent code name: R600a) and butane (molecular formula: C4H10, chemical code name: HC600, refrigeration agent code name: R600); Its ratio range (weight percent) is: C2H4F2 C2H4F2 (HFC152a) is 65%～85%, and Trimethylmethane (HC600a) is 11%～29%, and butane (HC600) is 1%～9%.
A best proportioning of the present invention (weight percent) embodiment is: C2H4F2 C2H4F2 (HFC152a) is 75%, and Trimethylmethane (HC600a) is 20%, and butane (HC600) is 5%, and at this moment, the present invention is an azeotropic mixture, and its normal boiling point is-29.0 ℃.
Referring to Fig. 1, to be this refrigeration agent should approach the numerical value of CFC12 corresponding to the saturation pressure of identical temperature of saturation to a criterion of mixing medium that can CFC alternative 12 as far as possible, Fig. 1 provided the present invention (use among the figure--◆--expression) and temperature of saturation-saturation pressure curve comparison diagram of CFC12 (use among the figure--▲--represent).As seen from the figure; In the temperature range (35 ℃～+ 55 ℃) of whole cooling condition, saturation pressure of the present invention and CFC12 are quite approaching, especially performance of refrigerant systems are being influenced of paramount importance vaporization temperature (35 ℃～-15 ℃) interval, and both are almost completely consistent.
We know, when non-azeotropic mixed working medium is used for common refrigeration cycle, its refrigeration performance is inferior to the performance that the pure working medium (comprising azeotropic mixture) in the identical systems is shown, and, for the zeotrope refrigeration agent, must in production technique, think better of its fractionation (being the ratio difference of each component in liquid and vapor capacity), when preventing that the actual mixture ratio that fills from departing from specified proportioning, may cause the decline of system performance, and the non-flammable zeotrope of specified proportioning may generate flammable fractionation when taking place to leak.An outstanding advantage of the present invention is that it is a kind of azeotropic mixture under specific proportioning, can be regarded as a kind of pure working medium fully and treat equally in production technique, can be used as the direct perfusion type surrogate of CFC12.
Another crisis one Greenhouse effect of environment protection also are subjected to the whole world day by day and pay attention to, so the final surrogate of CFC12 only may be those Global warmings lower refrigeration agent of value GWP of diving.The present invention not only latent value ODP of ozone depletion is zero, and its Global warming is dived, and GWP is also very little for value, has only 110, is far superior to 1200 of HFC134a.So, the present invention be a kind of environmental pollution very less or the long-term surrogate of the basic more satisfactory CFC12 that does not pollute.
The present invention successively carries out test of many times and implements on many different models, different makers' CFC12 compressor.To verify the various performances of ratio range of the present invention and best proportioning thereof.Fig. 2 is and uses a Tai Jiaxibeila JBB1112 type R12 Totally-enclosed-type compressor, utilizes the present invention and the CFC12 coefficient of performance curve comparison diagram as refrigeration agent respectively.The operating mode that this test is implemented is: 32.2 ℃ of envrionment temperatures, and 32.2 ℃ of supercooling temperatures, 32.2 ℃ of suction temperatures, 54.4 ℃ of condensing temperatures, vaporization temperature are respectively-35 ℃ ,-30 ℃ ,-23.3 ℃ and-15 ℃, ℃ are standard condition wherein-23.3.Among the figure-◆-be trial curve of the present invention ,-■-then be the trial curve of CFC12, as can be seen from the figure: use refrigeration agent of the present invention, its coefficient of performance increases, and in addition, both refrigerating dutys, noise objective are suitable.
The present invention has also carried out the test of various proportionings on the Zanussi ZEL board M1260 type CFC12 compressor of Tianjin, its results list is as follows:
| HFC152a/ Trimethylmethane/butane | Temperature glide (℃) | Compression ratio | ||
| Best proportioning | 75/20/5 | 0 | 10.8 | 1.18 |
| Proportioning A | 77/19/4 | 0.3 | 10.9 | 1.18 |
| Proportioning B | 73/21/6 | 0.2 | 10.8 | 1.18 |
| Proportioning C | 66/27/7 | 1.4 | 10.8 | 1.15 |
| Proportioning D | 84/14/2 | 1.3 | 11.2 | 1.19 |
| Proportioning E | 80/11/9 | 0.7 | 10.9 | 1.18 |
By test-results as can be seen, proportioning of the present invention is when departing from best proportioning little (as proportioning A and proportioning B), and it not only keeps the azeotropic characteristic substantially, and also very little to the performance impact of compressor.This helps the present invention as the preparation of mixture refrigerant with the simplification of keeping in repair of the product processes control when using this mixture refrigerant and product; When proportioning departs from best proportioning when big (as proportioning C and proportioning D), this mixture still keeps nearly azeotropic characteristic, but efficient descends to some extent when the ratio of HFC152a is too small; When the ratio of HFC152a was excessive, compression ratio increased to some extent.In addition, relatively proportioning D and proportioning E are as can be known: suitably increase the ratio of butane, can reduce compression ratio and help prolonging the compressor life-span.
Obtain in the compressor test on the basis of satisfactory result, the present invention successively tests on CFC12 refrigerator that many different models, different manufactory produce, ice box again, below shown in be to be embodiment with a new finesse BCD-206 household refrigerator-freezer, the current consumption that uses the present invention and CFC12 is numerical tabular relatively.
| Refrigeration agent | CFC12 | Refrigeration agent of the present invention (directly filling) | Refrigeration agent of the present invention (system's adjustment) |
| Refrigerating chamber medial temperature ℃ | 5.0 | 5.0 | 5.0 |
| Refrigeration chamber hottest spot temperature ℃ | -18.3 | -18.3 | -18.6 |
| Duty factor | 35.5％ | 34.8％ | 33.1％ |
| Current consumption kWh/24h | 1.05 | 1.03 | 0.95 |
Last table is listed respectively and is directly filled CFC alternative 12 and different current consumption through CFC alternative 12 after the suitable Adjustment System, and the latter reduces by power consumption 5% or more than the former, also wants power saving than the refrigerator of use CFC12 and directly fill alternate.This example explanation, if optimization design is exclusively used in refrigeration system of the present invention again, the energy-conservation of refrigerator also has suitable potentiality can supply to excavate.
The applicant has also carried out reaching the current consumption tracking test of half a year to two refrigerators wherein, do not find the trend that current consumption increases.This also explanation once more from the practice, the mineral lubricating oils of the present invention and former CFC12 refrigeration system is compatible fully, otherwise, understand former thereby cause the obvious increase of current consumption because of heat exchanger generation lubricating oil accumulation etc.
In a word, the direct perfusion type that the present invention can be used for the CFC12 refrigerator refrigerant substitutes, and the main performance index of this refrigerator is reached or is better than original parameter, has quite tempting social benefit and economic benefit.
Claims (2)
1, the azeotropic mixture refrigerant in a kind of replacement fluorine Lyons 12, it is characterized in that: it is a kind of mixture, and its weight moiety (weight percent) is: C2H4F2 C2H4F2 is 65%～85%, and Trimethylmethane is 11%～29%, and butane is 1%～9%.
2, the azeotropic mixture refrigerant in a kind of replacement fluorine as claimed in claim 1 Lyons 12 is characterized in that: an one best proportioning (weight percent) is: C2H4F2 C2H4F2 is 75%, and Trimethylmethane is 20%, and butane is 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101170 CN1070220C (en) | 1998-04-08 | 1998-04-08 | Azeotropic mixture refrigerant used as substitut for freon 12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98101170 CN1070220C (en) | 1998-04-08 | 1998-04-08 | Azeotropic mixture refrigerant used as substitut for freon 12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231323A CN1231323A (en) | 1999-10-13 |
| CN1070220C true CN1070220C (en) | 2001-08-29 |
Family
ID=5216515
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98101170 Expired - Fee Related CN1070220C (en) | 1998-04-08 | 1998-04-08 | Azeotropic mixture refrigerant used as substitut for freon 12 |
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|---|---|
| CN (1) | CN1070220C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457850C (en) * | 2006-06-26 | 2009-02-04 | 浙江蓝天环保高科技股份有限公司 | CFC-12 substituting environmental-protective cryogen |
-
1998
- 1998-04-08 CN CN 98101170 patent/CN1070220C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1231323A (en) | 1999-10-13 |
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| CF01 | Termination of patent right due to non-payment of annual fee |