KR20060009186A - Low temperature alternative refrigerant mixture - Google Patents
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Abstract
본 발명은 지구의 오존층 파괴와 지구온난화를 일으키는 원인으로 알려진 CFC계 냉매성분 R-115와 HCFC-22 의 혼합냉매인 R-502를 대체하는 저온용 대체 혼합냉매에 관한 것이다.The present invention relates to a low-temperature replacement mixed refrigerant replacing R-502, a mixed refrigerant of CFC-based refrigerant components R-115 and HCFC-22, known to cause global ozone layer destruction and global warming.
이를 위해 본 발명은, 메탄계 냉매성분인 디플로로메탄(CH2F2, 이하 R-32)과, 프로판(CH3CH2CH3, 이하 R-290), 프로필렌 (CH3CH=CH2 , 이하 R-1270)이 혼합되어 조성되며, 그 조성비는 메탄계 냉매성분인 디플로로메탄(CH2F2) 5~40 중량 %와, 프로판(CH3CH2CH3) 35~70 중량 %와, 프로필렌 (CH3CH=CH2 ) 25~60 중량 %가 전체 100 중량 %에 대해 혼합되어 조성된 것을 특징으로 하는 저온용 혼합냉매를 제공한다.To this end, the present invention, methane-based refrigerant dichloromethane (CH 2 F 2 , hereinafter R-32), propane (CH 3 CH 2 CH 3 , hereinafter R-290), propylene (CH 3 CH = CH 2 , hereinafter R-1270) is mixed, the composition ratio is 5 to 40% by weight of dichloromethane (CH 2 F 2 ) which is a methane-based refrigerant component, propane (CH 3 CH 2 CH 3 ) 35 ~ 70 It provides a low-temperature mixed refrigerant, characterized in that the weight% and 25 to 60 weight% of propylene (CH 3 CH = CH 2 ) is mixed with respect to the total 100 weight%.
탄화수소냉매, 혼합냉매, 냉동능력, 성능계수Hydrocarbon refrigerant, mixed refrigerant, freezing capacity, coefficient of performance
Description
본 발명은 저온용 대체 혼합냉매에 관한 것으로써, 상세하게는 지구의 오존층 파괴와 지구온난화를 일으키는 원인으로 알려진 CFC계 냉매성분 R-115와 HCFC-22 의 혼합냉매인 R-502를 대체하는 혼합냉매 조성물에 관한 것이다.The present invention relates to a low temperature alternative mixed refrigerant, and in particular, a mixed refrigerant replacing R-502, which is a mixed refrigerant of CFC-based refrigerant components R-115 and HCFC-22, known to cause global ozone layer destruction and global warming. It relates to a composition.
냉동사이클에서 사용되는 냉매는 증발기의 저온저압상태에서 증발하여 주위의 증발열을 흡수하고 압축기를 거치면서 고온고압의 기체로 압축되어, 액체상태로 된 냉매가 팽창밸브를 통과하여 감압되고 증발기로 순환함으로써 연속적으로 냉동작용을 한다.The refrigerant used in the refrigeration cycle is evaporated at low temperature and low pressure of the evaporator to absorb the heat of evaporation of the surroundings and is compressed into a gas of high temperature and high pressure through the compressor, the liquid refrigerant is decompressed through the expansion valve and circulated to the evaporator Continuously freezes.
이와 같은 냉동작용에서 중요한 역할을 하는 냉매는 냉동시키고자 하는 온도에 따라 고온용, 중온용, 저온용으로 나뉘며 저온용의 경우 -35 ~ -15 ℃의 범위에서 사용된다.Refrigerant that plays an important role in such a freezing action is divided into high temperature, medium temperature, and low temperature according to the temperature to be frozen, and is used in the range of -35 ~ -15 ℃ for low temperature.
R-22는 -10 ~ 10 ℃ 에서 사용되는 고온용 냉매의 대표적인 물질로, 냉매로 서 우수한 열역학적 특성과 독성이 없고 안전하여 가정용 및 산업용으로 널리 사용되고 있다.R-22 is a representative material of the high temperature refrigerant used at -10 ~ 10 ℃, it is widely used in household and industrial because of its excellent thermodynamic properties, nontoxic and safe.
R-22를 저온냉동기에 이용할 때는 압축비가 커지고 압축기 토출 온도가 증가하여 성능과 효율이 감소하는 특성이 있어서, 이를 보완하기 위해 R-22 : R-115를 48.8 : 51.2 중량%로 혼합한 R-502가 만들어졌다.When R-22 is used in a low temperature freezer, the compression ratio is increased and the compressor discharge temperature is increased to decrease the performance and efficiency.To compensate for this, R-22: R-115 mixed with 48.8: 51.2 wt% 502 was created.
상기된 R-502는 성능이 우수하고 취급이 편리하며 공비혼합물의 특성으로 산업용 저온냉동기에 널리 사용되어왔으나, 지구 온난화와 오존층 파괴를 일으키는 냉매성분이 포함되어 있어서 이를 대체할 물질의 연구가 진행되고 있다.R-502 described above has been widely used in industrial low temperature freezers because of its superior performance, convenient handling, and azeotrope, but it contains refrigerant components that cause global warming and destruction of ozone layer. have.
이와 같은 연구의 진행결과, 지금까지 개발된 대체냉매물질은 냉동성능과 친환경적 면을 동시에 만족시킬 수 있는 물질이 없으며, 특히 기존의 냉동기의 대폭적인 설계변경이 요구되어 추가적인 고비용이 발생되는 문제점이 있다.As a result of such research, the alternative refrigerant material developed so far has no material that can satisfy the freezing performance and eco-friendliness at the same time, and in particular, there is a problem that an additional high cost is required due to the significant design change of the existing refrigerator. .
본 발명은 상기된 문제점을 해소하기 위해 창안된 것으로써, R-502를 냉매로 사용하는 기존 냉동기의 설계변경을 최소화하고 친환경적인 혼합냉매를 구현한 저온용 대체 혼합냉매를 제공함에 그 목적이 있다.
The present invention has been made in order to solve the above problems, the object of the present invention is to provide a low-temperature alternative mixed refrigerant that minimizes the design change of the existing refrigerator using R-502 as a refrigerant and implements an environmentally friendly mixed refrigerant. .
상기 목적을 달성하기 위해 본 발명은 오존층 파괴와 지구온난화의 원인이 되는 CFC계 냉매인 R-502의 대체물질로서 혼합냉매를 조성하게 된다.In order to achieve the above object, the present invention provides a mixed refrigerant as an alternative to R-502, a CFC refrigerant that causes ozone layer destruction and global warming.
구체적으로, 본 발명은 메탄계 냉매성분인 디플로로메탄(CH2F2, 이하 R-32)과, 프로판(CH3CH2CH3, 이하 R-290), 프로필렌 (CH3CH=CH2 , 이하 R-1270)이 혼합되어 조성되며, 그 조성비는 메탄계 냉매성분인 디플로로메탄(CH2F2) 5~40 중량 %와, 프로판(CH3CH2CH3) 35~70 중량 %와, 프로필렌 (CH3CH=CH2 ) 25~60 중량 %가 전체 100 중량 %에 대해 혼합되어 조성된 것을 특징으로 한다.Specifically, the present invention is dichloromethane (CH 2 F 2 , hereinafter R-32), methane-based refrigerant component, propane (CH 3 CH 2 CH 3 , hereinafter R-290), propylene (CH 3 CH = CH 2 , hereinafter R-1270) is mixed, the composition ratio is 5 to 40% by weight of dichloromethane (CH 2 F 2 ) which is a methane-based refrigerant component, propane (CH 3 CH 2 CH 3 ) 35 ~ 70 Weight% and 25 to 60 weight% of propylene (CH 3 CH = CH 2 ) is characterized in that the composition is mixed with respect to 100% by weight.
<실시예><Example>
상기된 냉매에 필요한 조건은 기능적인 면에서는 적절한 비등점(임계온도)와 큰 잠열을 갖는 것이며, 또한, 실제 사용할 때 제일 중요한 요건은 안전으로 불연성이 무엇보다 추구되어왔다.The conditions necessary for the above-mentioned refrigerant have a suitable boiling point (critical temperature) and a great latent heat in terms of function, and the most important requirement in practical use has been safety incombustibility.
더불어, 다른 안전 면에서 독성이 없을 것, 기기의 사용면에서 열분해나 화학분해 되기 어려운 안정된 물질일 것, 냉동기유와 잘 용해되고 혼합냉매의 경우, 조성이 변하지 않는 것을 추구해 왔으며, 나아가 대체화의 원인이 되는 환경에의 영향이 적을 것, 제조 비용이 적을 것 등도 중요한 요건이다.In addition, it has been pursued to be non-toxic in terms of safety, to be a stable material that is difficult to be pyrolyzed or chemically decomposed in terms of use of the device, to be well dissolved with refrigeration oil, and to have a composition that does not change in the case of a mixed refrigerant. It is also an important requirement to have a low environmental impact and a low manufacturing cost.
또한, 상기 비등점은 대체냉매의 기능면에서 하나의 지표가 된다. 이것을 기준으로 하여 후보물질이 되는 탄화수소(탄소원자와 수소원자에서 비롯된 화합물) 이다. 비등점이 0 ~ -50 ℃ 정도의 탄화수소에는 프로필렌(비등점 -48℃), 프로판(비등점 -45℃), 이소부탄(비등점 -10℃), 부탄(비등점 -1℃) 등의 보조화합물이 있다.In addition, the boiling point is an indicator in terms of the function of the alternative refrigerant. Hydrocarbons (compounds derived from carbon and hydrogen atoms) are candidate substances on this basis. Hydrocarbons having a boiling point of 0 to -50 ° C include auxiliary compounds such as propylene (boiling point -48 ° C), propane (boiling point -45 ° C), isobutane (boiling point -10 ° C) and butane (boiling point -1 ° C).
탄화수소냉매는 표 1에서와 같이 단위중량당 잠열이 크고 액체상태의 비중이 작으므로 다른 냉매와 비교하여 충진량이 적고, 불소냉매와 비교해서도 냉동능력이 작지 않으며, 가격도 석유의 부산물이므로 비교적 저렴하다는 특징이 있으나, 최대 결점으로 연료로 사용될 정도로 연소성이 있는 것이다.Hydrocarbon refrigerants have a low latent heat per unit weight and a small specific gravity in liquid state, as shown in Table 1, and thus have less filling than other refrigerants. It is characterized by the fact that it is combustible enough to be used as a fuel as its biggest drawback.
그런 단점에도 불구하고, 친환경적인 냉매로 인식되어 유럽연합에서의 탄화수소계 냉매의 사용이 증가되고 현재 약 50%에 달하는 냉동 및 냉장장치에 이용되고 있다. 일본에서도 2002년부터 탄화수소냉매를 사용한 냉장고가 시판되기 시작했고, 국내의 가전업체에서도 수출용으로 생산하고 있다. Despite these drawbacks, they are recognized as environmentally friendly refrigerants, increasing the use of hydrocarbon-based refrigerants in the European Union and are currently being used in refrigeration and refrigeration units of up to 50%. In Japan, refrigerators using hydrocarbon refrigerants have been on the market since 2002, and domestic consumer electronics companies are producing them for export.
이 같은 탄화수소계의 냉매는 다음과 같은 잇점이 있다.Such hydrocarbon-based refrigerants have the following advantages.
- 단위 중량당 잠열이 크다. -Latent heat per unit weight.
- 탄화수소는 산(酸)을 형성하지 않으므로 배관 내 녹이 슬지 않는다.-Hydrocarbons do not form acid, so they will not rust in the pipe.
- HFC계 냉매와 비교하여 탄화수소는 비중이 60%나 적어서 냉매의 사용량이 줄어든다.Compared to HFC refrigerants, hydrocarbons have a specific gravity of 60%, which reduces the amount of refrigerant used.
- 에너지의 효율이 15-20% 향상된다.Energy efficiency is improved by 15-20%.
- 석유의 부산물이므로 가격이 비교적 저렴하다.-It is a relatively low price because it is a by-product of oil.
- 오존층을 파괴하지 않으며, 지구온난화에 영향을 주지 않는다. -Does not destroy the ozone layer and does not affect global warming.
탄화수소계 냉매의 단점인 연소성을 회피하기 위한 방편으로, 불연물과 혼합하거나 분자의 구조를 변화시키는 방법이 있다.As a way to avoid the combustibility of the hydrocarbon-based refrigerant, there is a method of mixing with the incombustibles or changing the structure of the molecule.
상기된 단점은 탄화수소가 타기 쉬운 것은 탄소와 수소의 결합 때문이다. 타기 쉬운 정도를 전기음성도라는 지표로 보면 표 2에서와 같이 수소는 전기음성도가 2.1 로 탄소의 2.5보다 작고, 수소와 결합된 탄소는 태울 수 있는 상태(환원상태)가 된다. 탄다는 것은 탄소가 산화되는 것으로 탄소가 전기음성도가 3.5로 큰 산소와 결합하는 것이다. 산소와 결합한 탄소는 산화상태 즉 탄소가스(CO2)로 이 이상은 타지 않는다. 이와 같이 탄화수소를 타기 어렵게 하기 위해서 산소와 같이 전기음성도가 큰 원자를 결합하면 된다.The above mentioned disadvantage is that the hydrocarbon is easily burned because of the bonding of carbon and hydrogen. In terms of the degree of burnability as an index of electronegativity, hydrogen has an electronegativity of 2.1, which is less than 2.5 of carbon, and carbon combined with hydrogen is in a burnable state (reduced state). Burning means that the carbon is oxidized, and the carbon combines with oxygen with an electronegativity of 3.5. Carbon combined with oxygen is in an oxidized state, that is, carbon gas (CO 2 ). In order to make it hard to burn a hydrocarbon in this way, what is necessary is just to combine the atom with high electronegativity, such as oxygen.
따라서, 본 발명에서와 같이 탄화수소 냉매 혼합물의 가연성을 개선하기 위해 전기음성도가 비교적 높아서 연소성을 회피할 수 있는 CO2를 첨가제로 쓰거나, 전기음성도가 높은 원소를 포함하는 냉매성분을 혼합하는 것이 바람직하다.Therefore, in order to improve the flammability of the hydrocarbon refrigerant mixture as described in the present invention, it is preferable to use CO 2 as an additive which can avoid combustibility due to a relatively high electronegativity or to mix a refrigerant component containing a high electronegativity element. desirable.
결국, 본 발명의 실시예에서 혼합냉매의 조성물은 탄화수소계에서 선택되는 냉매의 혼합물로 탄화수소계의 2성분과 탄화수소계의 연소성을 개선하기 위해 HFC계에서 선택되는 냉매의 3성분 혼합냉매 조성에 의해 구현된다.As a result, the composition of the mixed refrigerant in the embodiment of the present invention is a mixture of the refrigerant selected from the hydrocarbon system by the three-component mixed refrigerant composition of the refrigerant selected from the HFC system to improve the combustibility of the hydrocarbon-based two-component and hydrocarbon-based Is implemented.
참고적으로, 냉매의 열역학적 특성을 보면 기존의 저온용 냉매인 R-502는 냉동능력이 우수하나 환경규제대상물질이다. 대체냉매로 사용되고 있는 R-404A는 오존층 파괴지수 (ODP)는 0이지만, 여전히 지구온난화지수가 커서 완전한 대체냉매라고 할 수 없다. For reference, in view of the thermodynamic characteristics of the refrigerant, the existing low-temperature refrigerant R-502 has excellent refrigeration capacity but is an environmentally regulated material. R-404A, which is used as an alternative refrigerant, has an Ozone Depletion Index (ODP) of zero, but still has a global warming index, making it an alternative.
표 3은 본 발명에 의한 혼합냉매 조성을 R-32 : 290 : 1270 가 10 : 60 : 30 (각 중량 %)일 때 조성 1로, 10 : 50: 40 (각 중량 %)를 조성 2로, 5 : 65 : 30 (각 중량 %) 일 때의 경우를 조성 3으로 하여서 된 조성물을 얻은 후, 이를 기존의 냉매와 열역학적 성질을 대비실험하여 비교한 것이다.Table 3 shows the composition 1 of the mixed refrigerant composition according to the present invention as composition 1 when R-32: 290: 1270 is 10:60:30 (each weight%), and 10:50:40 (each weight%) as composition 2,5 : 65: 30 (each weight%) The composition obtained by the composition 3 is obtained, and compared with the conventional refrigerant and thermodynamic properties by comparison experiment.
본 발명에 의한 혼합냉매조성은 R-502와 기존의 대체냉매인 R-404A와 비교하여 분자량이 작고증발잠열이 높아서 냉매사용량을 절감할 수 있으며 특히, 오존층 파괴지수(ODP)가 0이며 지구온난화지수 (GWP)가 100 이하인 점에서 매우 우수한 친환경적인 특성을 가지고 있다. The mixed refrigerant composition according to the present invention can reduce refrigerant consumption due to its low molecular weight and high evaporative latent heat compared to R-502 and R-404A, which is a conventional alternative refrigerant, and in particular, the ozone layer destruction index (ODP) is 0 and global warming. It has very good eco-friendly characteristics in that the index (GWP) is 100 or less.
R-502 대체냉매로 제안한 본 발명을 산업용 냉동기, 쇼케이스 등 저온용으로 이용할 수 있는지 검토하기 응축 및 증발압력, 냉매유량, 압축비, 성적계수 등의 이론 사이클 특성 해석을 수행하였다. 이를 위한 조건은 표 4와 같이 ASHARE의 LBP(low back pressure)로 하였으며, 그 결과는 표 5에서와 같다.Investigating whether the present invention proposed as R-502 alternative refrigerant can be used for low temperature, such as industrial refrigerator, showcase, etc. The theoretical cycle characteristics analysis such as condensation and evaporation pressure, refrigerant flow rate, compression ratio, and performance coefficient were performed. The conditions for this were as LBP (low back pressure) of ASHARE as shown in Table 4, the results are shown in Table 5.
냉매의 물성치 계산은 미국 NIST의 냉매물성치 프로그램(Refprop 6.01)을 이용하였다. 각 조성에 대해 p-h 선도상에서 주어진 조건의 사이클을 그린 후, 각 점에서의 상태를 찾아내어 증발과 응축압력, 온도구배, 체적냉동능력, 성능계수 등을 상호 비교하였다.The properties of the refrigerants were calculated using the NIST refrigerant properties program (Refprop 6.01). After plotting the given conditions on the p-h plot for each composition, the states at each point were found and compared with each other for evaporation, condensation pressure, temperature gradient, volume freezing capacity and performance coefficient.
상기된 이론 사이클 해석결과를 보면, 본 발명의 혼합냉매 조성물은 R-502보다 증발압력이 30% 정도 높으나, 응축압력은 같은 수준으로 증발 및 응축과정에서 온도구배가 나타나는 전형적인 비공비 냉매의 특성을 보인다. 본 발명의 냉매조성물은, 혼합비율 변화에 따라 증발과 응축과정에서 온도구배는 4.3 ~ 8.3 ℃ 까지 변하였다. According to the theoretical cycle analysis results, the mixed refrigerant composition of the present invention has a 30% higher evaporation pressure than R-502, but the condensation pressure is the same level, the characteristics of typical non-azeotropic refrigerants exhibiting a temperature gradient during evaporation and condensation. see. The refrigerant composition of the present invention, the temperature gradient during the evaporation and condensation process was changed to 4.3 ~ 8.3 ℃ according to the mixing ratio change.
같은 조건에서, 현재 사용중인 HFC계 비공비 혼합냉매 R-407C (R-32:R-125:R-134a = 23:25:52 중량 %) 의 응축과 증발과정의 온도구배가 4.3 ~ 4.4 ℃인 것과 비교된다.Under the same conditions, the temperature gradient of the condensation and evaporation process of the currently used HFC azeotropic mixed refrigerant R-407C (R-32: R-125: R-134a = 23:25:52 weight%) is 4.3-4.4 ° C. Is compared to
본 발명의 냉매조성물은 현재 대체 대상인 R-502에 비해 증발과 응축의 압축비가 작아서 압축기 소요동력이 낮아지며, 체적냉동능력이 20% 정도 상승된다. 그리고 시스템의 성능계수가 10% 이상 향상되어 소비에너지를 절약 할 수 있다.The refrigerant composition of the present invention has a smaller compression ratio of evaporation and condensation than the current R-502, which reduces the power consumption of the compressor and increases the volume freezing capacity by about 20%. And the system's performance coefficient is improved by more than 10%, which saves energy consumption.
본 발명에 따른 저온용 혼합냉매 조성물을 이용할 경우, 지구환경파괴물질로 규제대상인 R-502 냉매를 대체하여 사용할 수 있으며, 냉매 혼합 조성에 따라서, 응축압력을 비롯한 냉동특성이 R-502와 유사하므로 기존 냉동기의 설계변경을 최소화 할 수 있다.When the low temperature mixed refrigerant composition according to the present invention is used, R-502 refrigerant, which is regulated as a global environmental destructive substance, may be used, and according to the refrigerant mixture composition, refrigeration characteristics including condensation pressure are similar to those of R-502. It is possible to minimize the design change of the existing refrigerator.
또한, 본 발명은 체적냉동능력이 커서 냉동기에 충진하는 냉매의 사용량을 줄일 수 있어서 냉동기제품의 제조원가 절감을 기대할 수 있으며, 냉동능력이 기존냉매 대비 우수하여 냉동기의 운전비용을 줄일 수 있다.
In addition, the present invention can reduce the amount of refrigerant to be filled in the refrigerator due to the large volume freezing capacity can be expected to reduce the manufacturing cost of the freezer product, the freezing capacity is superior to the existing refrigerant can reduce the operating cost of the freezer.
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