KR20020064026A - Refrigerant composition containing difluoromethane, 1,1,1-trifluoroethane and 1,1-difluoroethane - Google Patents
Refrigerant composition containing difluoromethane, 1,1,1-trifluoroethane and 1,1-difluoroethane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K5/044—Materials 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
- C09K5/045—Materials 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 containing only fluorine as halogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
- F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
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Abstract
Description
본 발명은 지구의 오존층을 파괴하는 것으로 알려진 클로로디플루오로메탄 (CHClF2, 이하 HCFC-22)을 대체하기 위한 냉매 조성물에 관한 것이다.The present invention relates to a refrigerant composition for replacing chlorodifluoromethane (CHClF 2 , hereafter HCFC-22) known to destroy the earth's ozone layer.
CFC 화합물은 이미 잘 알려진 바와 같이 지구의 오존층을 파괴하는 물질로 밝혀짐에 따라 몬트리올 의정서에 의해 그 생산과 사용이 규제를 받고 있으며 선진국에서는 1996년부터 이미 사용이 금지된 상태이다. 그리고, CFC 화합물의 대체물질로 개발된 HCFC-22를 비롯한 HCFC계열의 화합물도 CFC 화합물만큼 심하지는 않으나 오존층을 파괴하는 것으로 알려져 점차 그 사용량을 규제하여 2030년경부터는 사용이 전면적으로 금지될 예정이다.The production and use of CFC compounds has been regulated by the Montreal Protocol as it is already known to destroy the earth's ozone layer and has been banned since 1996 in developed countries. In addition, HCFC-based compounds, including HCFC-22, developed as substitutes for CFC compounds, are not as severe as CFC compounds, but are known to destroy the ozone layer, and their usage is gradually regulated.
따라서, HCFC-22의 대체물질 개발에 대하여 많은 연구가 이루어지고 있으며 대표적으로는 미국냉동공조학회(ASHRAE)의 HFC-407C와 HFC-410A를 들 수가 있다. 여기에서, HFC-407C는 HFC-32/125/134a가 23/25/52의 중량%로 혼합된 냉매 조성물이고, HFC-410A는 HFC-32/125가 50/50의 중량%로 혼합된 냉매 조성물이다.Therefore, a lot of research is being conducted on the development of alternatives to HCFC-22, and representative examples are HFC-407C and HFC-410A of the American Society of Refrigeration and Air Conditioning (ASHRAE). Here, HFC-407C is a refrigerant composition in which HFC-32 / 125 / 134a is mixed at 23/25/52 wt%, and HFC-410A is refrigerant in which HFC-32 / 125 is mixed at 50/50 wt% Composition.
이 밖에, 미국특허 제5,080,823호에는 HFC-143a/Propane이, 미국특허 제5,211,867호에는 HFC-125/143a가, 미국특허 제5,234,613호에는 HFC-32/Propane이, 미국특허 제5,236,611호에는 PFC-218/HFC-143a가, 미국특허 제5,290,466호에는 HFC-32/134a/134가, 미국특허 제5,340,490호에는 HFC-23/CO2와 HFC-23/116/CO2가, 미국특허 제5,403,504호에는 HFC-125/32가, 미국특허 제5,429,740호에는 HFC-23/134a가, 미국특허 제5,538,660호에는 HFC-32/HFC-134a/FC-41과 HFC-32/HFC-134a/PFC-218이, 미국특허 제5,643,492호에는 HFC-32/125/134a가 냉매 조성물로 각각 개시되어 있다.In addition, US Patent No. 5,080,823, HFC-143a / Propane, US Patent No. 5,211,867, HFC-125 / 143a, US Patent No. 5,234,613, HFC-32 / Propane, US Patent No. 5,236,611 PFC- 218 / HFC-143a, HFC-32 / 134a / 134 in U.S. Patent 5,290,466, HFC-23 / CO 2 and HFC-23 / 116 / CO 2 in U.S. Patent 5,340,490, U.S. Patent 5,403,504 Is HFC-125 / 32, US Patent No. 5,429,740 is HFC-23 / 134a, US Patent No. 5,538,660 is HFC-32 / HFC-134a / FC-41 and HFC-32 / HFC-134a / PFC-218 In this US Pat. No. 5,643,492, HFC-32 / 125 / 134a is disclosed as a refrigerant composition, respectively.
또한, 일본공개특허 특개평3-172386호에는 HFC-32/125/143a가, 특개평3-170594호에는 HFC-23/125/134a가, 특개평3-170593호에는 HFC-23/125/32와 HFC-23/143a/134a가, 특개평3-170590호에는 HFC-125/134a/32가, 특개평3-170589호에는 HFC-23/143a/152a가, 특개평3-170588호에는 HFC-125/143a/134a가, 특개평3-170585호에는 HFC-32/125/134a가, 특개평3-170584호에는 HFC-23/134a/152a가, 특개평3-170583호에는 HFC-125/143a/32가, 특개평4-222893호에는 HFC-32/125가, 특개평4-154887호에는 HFC-134/152a가, 특개평5-117645호에는 HFC-23/134a/Propane이, 특개평5-117643호에는 HFC-125/134a/Propane이, 특개평6-65561호에는 HFC-23/152a/PFC-218이, 특개평6-128872호에는 HFC-32/PFC-218이, 특개평6-220433호에는 HFC-32/125/RC-318이, 특개평7-173462호에는 HFC-143a/125/134a/Heptane이, 특개평8-176537호에는 PFC-218/RC-270/HFC-152a가, 특개평8-151569호에는 Propane/RC-270/HFC-134a가, 특개평8-127767호에는 HFC-32/134a/RC-318이, 특개평9-25480호에는 HFC-32/134a/125/Isobutane이, 특개평9-59611호에는 HFC-134a/Isobutane이, 특개평9-208941호에는 HFC-32/152a/125/RC-270이, 특개평9-221664호에는 HFC-125/143a/134a/RC-270이 각각 새로운 냉매 조성물로 개시되어 있다.In addition, Japanese Patent Laid-Open No. 3-172386, HFC-32 / 125 / 143a, Japanese Patent Laid-Open No. 3-170594, HFC-23 / 125 / 134a, and Japanese Patent Laid-Open No. 3-170593 are HFC-23 / 125 / 32 and HFC-23 / 143a / 134a, HFC-125 / 134a / 32 in Japanese Patent Application Laid-Open No. 3-170590, HFC-23 / 143a / 152a in Japanese Patent Application Laid-Open No. 3-170589, and Japanese Patent Application Laid-Open No. 3-170588. HFC-125 / 143a / 134a, HFC-32 / 125 / 134a in Japanese Patent Application Laid-Open No. 3-170585, HFC-23 / 134a / 152a in Japanese Patent Application Laid-Open No. 3-170584, and HFC- 125 / 143a / 32, HFC-32 / 125 in JP-A-4-222893, HFC-134 / 152a in JP-A 4-154887, and HFC-23 / 134a / Propane in JP-A 5-117645. HFC-125 / 134a / Propane in Japanese Patent Laid-Open No. 5-117643, HFC-23 / 152a / PFC-218 in Japanese Laid-Open Patent Publication No. 6-65561, HFC-32 / PFC-218 in Japanese Laid-Open Publication No. 6-128872 HFC-32 / 125 / RC-318 in Japanese Patent Application Laid-Open No. 6-220433, HFC-143a / 125 / 134a / Heptane in Japanese Patent Application Laid-Open No. 7-173462, and PFC-218 / RC- in Japanese Patent Application Laid-Open No. 8-176537. 270 / HFC-152a, Propane / RC-270 / HFC-134a in Japanese Patent Laid-Open No. 8-151569, and Japanese Patent Laid-Open No. 8-127767 HFC-32 / 134a / RC-318, HFC-32 / 134a / 125 / Isobutane in Japanese Patent Laid-Open No. 9-25480, HFC-134a / Isobutane in Japanese Patent Laid-Open No. 9-59611, and Japanese Patent Laid-Open No. 9-208941. HFC-32 / 152a / 125 / RC-270 and Japanese Patent Laid-Open No. 9-221664 disclose HFC-125 / 143a / 134a / RC-270 as new refrigerant compositions, respectively.
또한, 한국등록특허 제93-10514호에는 HFC-23/32/152a, HFC-23/125/152a, HFC-32/143a/152a, HFC-125/143a/152a, HFC-32/125/125a, HFC-23/143a/152a 및 HFC-23/125/152a가, 제93-10515호에는 HFC-23/32/134, HFC-23/32/134a, HFC-23/125/134, HFC-32/125/134, HFC-23/143a/134a, HFC-23/143a/134a, HFC-125/143a/134a 및 HFC-125/143a/134가, 한국공개특허 제96-4485호에는 HFC-32/23/134a가, 한국공개특허 제96-701168호에는 HFC-227ea/HFC-152a가, 한국공개특허 제97-704853호에는 HFC-134a/HCFC-124/Butane이 각각 개시되어 있다.In addition, Korean Patent No. 93-10514 discloses HFC-23 / 32 / 152a, HFC-23 / 125 / 152a, HFC-32 / 143a / 152a, HFC-125 / 143a / 152a, HFC-32 / 125 / 125a , HFC-23 / 143a / 152a and HFC-23 / 125 / 152a, H93-23 / 32/134, HFC-23 / 32 / 134a, HFC-23 / 125/134, HFC- 32/125/134, HFC-23 / 143a / 134a, HFC-23 / 143a / 134a, HFC-125 / 143a / 134a and HFC-125 / 143a / 134 are disclosed in Korean Patent Laid-Open No. 96-4485. 32/23 / 134a discloses HFC-227ea / HFC-152a in Korean Patent Publication No. 96-701168 and HFC-134a / HCFC-124 / Butane in Korean Patent Publication No. 97-704853, respectively.
본 발명의 목적은 지구의 오존층을 파괴하는 물질이 함유되지 않은, HCFC-22를 대신하여 사용할 수 있는 새로운 냉매 조성물을 제공하는 것이다.It is an object of the present invention to provide a novel refrigerant composition that can be used in place of HCFC-22, which does not contain substances that destroy the earth's ozone layer.
상기 목적을 달성하기 위한 본 발명의 냉매 조성물은The refrigerant composition of the present invention for achieving the above object
디플루오로메탄(CH2F2, 이하 HFC-32)과;Difluoromethane (CH 2 F 2 , hereinafter HFC-32);
1,1,1-트리플루오로에탄(CH3CF3, 이하 HFC-143a)과;1,1,1-trifluoroethane (CH 3 CF 3 , hereafter HFC-143a);
1,1-디플루오로에탄(CH3CHF2, 이하 HFC-152a)과;1,1-difluoroethane (CH 3 CHF 2 , hereafter HFC-152a);
1,1,1,2,3,3,3-헵타플루오로프로판(CF3CHFCF3, 이하 HFC-227ea), 이소부탄(CH(CH3)2CH3, R-600a), 1,1,1,2,3,3-헥사플루오로프로판(CHF2CHFCF3, 이하 HFC-236ea), 및 부탄(C4H10, 이하 R-600)으로 이루어지는 군에서 선택되는 하나의 화합물로 이루어진다.1,1,1,2,3,3,3-heptafluoropropane (CF 3 CHFCF 3 , hereinafter HFC-227ea), isobutane (CH (CH 3 ) 2 CH 3 , R-600a), 1,1 And 1,2,3,3-hexafluoropropane (CHF 2 CHFCF 3 , hereinafter HFC-236ea), and butane (C 4 H 10 , hereinafter R-600).
이들 물질들은 오존층 파괴의 위험이 전혀 없어 향후에도 사용규제에 대한 우려가 없는 것이 장점이다. 또한, 상기 물질들은 이미 생산되고 있거나 차후 생산을 위한 연구가 활발히 진행중인 단계에 있으므로 본 발명을 통해 그 용도를 새로이 추가함으로써 보다 효율적인 활용이 가능하게 되었다.These substances have no risk of destroying the ozone layer, so there is no concern about future use restrictions. In addition, since the materials are already being produced or are being actively researched for production in the future, the present invention enables more efficient utilization by adding new uses.
본 발명에서는 상기의 혼합냉매 조성물을 압축기, 응축기, 팽창밸브 및 증발기로 이루어지는 냉동시스템에 적용하여 성능계수(COP), 냉매 단위체적당의 열량(VC), 압축기 및 증발기에서의 압력 등을 비교/검토하였다. 본 발명에서 제시하는 새로운 냉매 조성물은 대체냉매로 제시된 HFC-407C나 HFC-410과 비교하여 성능면에서 거의 같은 수준으로 평가되었으며 HCFC-22의 대체물질로 유용하게 사용될 수 있다. 본 발명의 냉매 조성물의 조성비는 다음과 같다.In the present invention, the mixed refrigerant composition is applied to a refrigeration system including a compressor, a condenser, an expansion valve, and an evaporator, and compares / reviews the coefficient of performance (COP), the amount of heat per unit volume of refrigerant (VC), the pressure in the compressor, and the evaporator. It was. The new refrigerant composition proposed in the present invention was evaluated at about the same level of performance as HFC-407C or HFC-410 proposed as a replacement refrigerant, and can be usefully used as a substitute for HCFC-22. The composition ratio of the refrigerant composition of the present invention is as follows.
상기 냉매 조성물에서 HFC-227ea를 포함하는 경우, HFC-32, HFC-143a, HFC-152a 및 HFC-227ea의 조성비는 순서대로 30∼70중량%, 10∼50중량%, 10∼40중량%,10∼30중량%가 되도록 하며, 바람직하게는 40∼60중량%, 20∼40중량%, 20∼30중량%, 15∼25중량%가 되도록 한다.When the refrigerant composition includes HFC-227ea, the composition ratio of HFC-32, HFC-143a, HFC-152a and HFC-227ea may be in the order of 30 to 70% by weight, 10 to 50% by weight, 10 to 40% by weight, 10 to 30% by weight, preferably 40 to 60% by weight, 20 to 40% by weight, 20 to 30% by weight, and 15 to 25% by weight.
상기 냉매 조성물에서 R-600a를 포함하는 경우, HFC-32, HFC-143a, HFC-152a 및 R-600a의 조성비는 순서대로 30∼70중량%, 10∼50중량%, 10∼40중량%, 5∼15중량%가 되도록 하며, 바람직하게는 40∼60중량%, 20∼40중량%, 20∼30중량%, 8∼12 중량%가 되도록 한다.When the refrigerant composition includes R-600a, the composition ratio of HFC-32, HFC-143a, HFC-152a, and R-600a may be in the order of 30 to 70 wt%, 10 to 50 wt%, 10 to 40 wt%, 5 to 15% by weight, preferably 40 to 60% by weight, 20 to 40% by weight, 20 to 30% by weight and 8 to 12% by weight.
상기 냉매 조성물에서 HFC-236ea를 포함하는 경우, HFC-32, HFC-143a, HFC-134a 및 HFC-236ea의 조성비는 순서대로 30∼70중량%, 10∼40중량%, 10∼40중량%, 10∼20중량%가 되도록 하며, 바람직하게는 20∼60중량%, 20∼30중량%, 20∼30중량%, 13∼17중량%가 되도록 한다.When HFC-236ea is included in the refrigerant composition, the composition ratio of HFC-32, HFC-143a, HFC-134a, and HFC-236ea may be in the order of 30 to 70% by weight, 10 to 40% by weight, 10 to 40% by weight, 10 to 20% by weight, preferably 20 to 60% by weight, 20 to 30% by weight, 20 to 30% by weight, and 13 to 17% by weight.
상기 냉매 조성물에서 R-600을 포함하는 경우, HFC-32, HFC-143a, HFC-134a 및 R-600의 조성비는 순서대로 30∼70중량%, 10∼40중량%, 10∼50중량%, 5∼12중량%가 되도록 하며, 바람직하게는 40∼60중량%, 20∼30중량%, 20∼40중량%, 7∼10 중량%가 되도록 한다.When the refrigerant composition includes R-600, the composition ratio of HFC-32, HFC-143a, HFC-134a, and R-600 is in the order of 30 to 70% by weight, 10 to 40% by weight, 10 to 50% by weight, 5 to 12% by weight, preferably 40 to 60% by weight, 20 to 30% by weight, 20 to 40% by weight, and 7 to 10% by weight.
본 발명의 구성은 냉매 조성물의 성능을 평가한 이하의 비교예 및 실시예를 통하여 더욱 명확해질 것이며 그 효과가 입증될 것이다.The construction of the present invention will become more apparent through the following comparative examples and examples in which the performance of the refrigerant composition is evaluated, and the effect thereof will be demonstrated.
<비교예 및 실시예>Comparative Examples and Examples
압축기, 응축기, 팽창밸브 및 증발기로 이루어지는 냉동 시스템을 사용하여 하기 조건에서 HCFC-22, HFC-407C, HFC-410A(비교예 1∼3)와 본 발명의 냉매 조성물(실시예 1∼4)에 대하여 냉매의 성능평가에 있어서 주요인자인 성능계수(COP),냉매 단위체적당의 열량(VC), 증발기 압력(PL) 및 응축기 압력(PH)을 비교하였다.Using a refrigeration system consisting of a compressor, a condenser, an expansion valve, and an evaporator, HCFC-22, HFC-407C, HFC-410A (Comparative Examples 1 to 3) and the refrigerant composition (Examples 1 to 4) of the present invention were In the evaluation of refrigerant performance, the main factors such as COP, calorie value per unit volume of refrigerant (VC), evaporator pressure (P L ) and condenser pressure (P H ) were compared.
(1) 냉방용량: 2 kW(1) Cooling capacity: 2 kW
(2) 증발기의 총열관류율(UA): 0.20 kW/K(2) Total heat transmission rate (UA) of evaporator: 0.20 kW / K
(3) 응축기의 총열관류율(UA): 0.24 kW/K(3) Total heat transmission rate (UA) of condenser: 0.24 kW / K
(4) 응축기에서의 과냉도: 5℃(4) supercooling in condenser: 5 ° C
(5) 증발기에서의 과열도: 5℃(5) superheat degree in evaporator: 5 ° C
(6) 압축기 효율: 0.8(6) compressor efficiency: 0.8
(7) 2차 유체의 응축기 입구온도: 25℃(7) condenser inlet temperature of secondary fluid: 25 ° C
(8) 2차 유체의 응축기 출구온도: 35℃(8) condenser outlet temperature of secondary fluid: 35 ° C
(9) 2차 유체의 증발기 입구온도: 15℃(9) Evaporator inlet temperature of secondary fluid: 15 ℃
(10) 2차 유체의 증발기 출구온도: 5℃(10) Evaporator outlet temperature of secondary fluid: 5 ℃
<비교예 1∼3><Comparative Examples 1 to 3>
상기 조건에서 HCFC-22와 HFC-407C와 HFC-410A에 대하여 성능을 평가하였으며 결과는 다음의 [표 1]에 기재하였다.Performance was evaluated for HCFC-22, HFC-407C and HFC-410A under the above conditions, and the results are shown in the following [Table 1].
[표 1]로부터 HFC-407C는 HCFC-22와 비교하여 COP는 약간 떨어지나 VC 및 압력은 거의 비슷함을 알 수 있고, HFC-410A의 경우는 COP는 비슷하고 VC는 우수하나 압력이 HCFC-22에 비해 다소 높음을 알 수 있다.From Table 1, HFC-407C shows a little drop in COP compared to HCFC-22, but VC and pressure are almost similar.For HFC-410A, COP is similar and VC is excellent, but pressure is HCFC-22. It is somewhat higher than.
그런데, 냉매의 성능이 이러한 범위 내에 있을 경우 HCFC-22의 대체냉매로서 사용이 가능한 것으로 평가되고 있으므로 후술하는 실시예에서는 이들 결과와 비교하였다.However, when the performance of the refrigerant falls within this range, it is evaluated that it can be used as an alternative refrigerant of HCFC-22. Thus, the examples described later were compared with these results.
<실시예 1><Example 1>
HFC-32/HFC-143a/HFC-152a/HFC-227ea로 이루어진 냉매 조성물의 조성변화에 따른 성능평가를 하였으며 결과를 [표 2]에 기재하였다.Performance evaluation according to the composition change of the refrigerant composition consisting of HFC-32 / HFC-143a / HFC-152a / HFC-227ea was performed and the results are shown in [Table 2].
각 항목별 성능이 대체냉매인 HFC-407C와 HFC-410A의 중간범위에 있어 HCFC-22 대체냉매로서 사용될 수 있음을 알 수 있다.It can be seen that the performance of each item can be used as an HCFC-22 alternative refrigerant in the intermediate range of the alternative refrigerants HFC-407C and HFC-410A.
<실시예 2><Example 2>
HFC-32/HFC-143a/HFC-152a/R-600a로 이루어진 냉매 조성물의 조성변화에 따른 성능평가 결과는 [표 3]과 같다.Performance evaluation results according to the composition change of the refrigerant composition consisting of HFC-32 / HFC-143a / HFC-152a / R-600a are shown in Table 3.
각 항목별 성능이 HFC-407C와 HFC-410A의 중간범위에 있으므로 HCFC-22 대체냉매로서 사용될 수 있음을 알 수 있다.Since the performance of each item is in the middle range of HFC-407C and HFC-410A, it can be seen that it can be used as a HCFC-22 alternative refrigerant.
<실시예 3><Example 3>
HFC-32/HFC-143a/HFC-152a/HFC-236ea로 이루어진 냉매 조성물의 조성변화에 따른 성능평가 결과는 [표 4]와 같다.Performance evaluation results according to the composition change of the refrigerant composition consisting of HFC-32 / HFC-143a / HFC-152a / HFC-236ea are shown in Table 4.
각 항목별 성능이 HFC-407C와 HFC-410A의 중간범위에 있어 HCFC-22 대체냉매로서 사용될 수 있음을 알 수 있다.It can be seen that the performance of each item can be used as HCFC-22 alternative refrigerant in the middle range of HFC-407C and HFC-410A.
<실시예 4><Example 4>
HFC-32/HFC-143a/HFC-152a/R-600로 이루어진 냉매 조성물의 조성변화에 따른 성능평가 결과는 [표 5]와 같다.Performance evaluation results according to the composition change of the refrigerant composition consisting of HFC-32 / HFC-143a / HFC-152a / R-600 is shown in Table 5.
각 항목별 성능이 HFC-407C와 HFC-410A의 중간범위에 있어 HCFC-22 대체냉매로서 사용될 수 있음을 알 수 있다.It can be seen that the performance of each item can be used as HCFC-22 alternative refrigerant in the middle range of HFC-407C and HFC-410A.
본 발명에 의하면 오존층 파괴의 위험이 전혀 없어 향후에도 사용규제에 대한 우려가 없다. 아울러, 상기 물질들은 이미 생산되고 있거나 차후 생산을 위한 연구가 활발히 진행중인 단계에 있으므로 본 발명을 통해 그 용도를 새로이 추가함으로써 보다 효율적인 활용이 가능하게 되었다.According to the present invention, there is no risk of ozone layer destruction, and there is no concern about use regulation in the future. In addition, since the materials are already being produced or are being actively researched for production in the future, the present invention enables more efficient utilization by adding new uses.
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