TWI686467B - 非臭氧消耗及低全球暖化冷媒摻合物 - Google Patents
非臭氧消耗及低全球暖化冷媒摻合物 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—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
- 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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- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
非臭氧消耗和非易燃的冷媒摻合物,其具有位於1,000和1,600之間的ITHGWP,並可於製冷系統中取代R404A和R507。
Description
本發明涉及冷媒摻合物。
例如CFC12和CFC502等氯氟烴(CFC)以及例如HCFC22等氫氯氟烴(HFC)會遷移到平流層,在該處它們被紫外線分解,產生破壞臭氧的氯原子。這些消耗臭氧物質(ODS)正在被非臭氧消耗的替代品取代,例如由氫氟烴(HFC)取代,其為非易燃、具高效益和低毒性的。在某些應用中(尤其但不限於涉及常用於超市中的低溫製冷系統的應用),曾被選用的冷媒以R502為主,這主要因為其排放溫度比R22低。在《蒙特利爾議定書》涵蓋的全球環境協議中,R502已被禁用。R502大體上已被R404A和R507這些HFC取代。但是,R404A和R507雖然在能源效益、非可燃性、低毒性及熱力學性質這些方面上皆為出色的冷媒,但其GWP仍處於常用的HFC中的高端。
本發明的目的在於提供冷媒摻合物,於100年的積分時間跨度(ITH)中,其具有的全球暖化潛能(GWP)超過1000但小於1600。在本說明書中,全球暖化潛能(GWP)的數值參照的積分時間跨度(ITH)為100年,如政府間氣候變化專門委員會(Inter-Governmental Panel on Climate Change)的第四次評估報告(AR4)所包含的,並對平流層臭氧沒有不良影響。本發明涉及摻合物,其特別是用於取代在製冷系統中的R404A和R507的摻合物(但不限於此),並且是非易燃的、具高效益和低毒性的。
本發明特別涉及的冷媒摻合物具有比R404A和R507低不少的GWP,但是非易燃的,且比替代的摻合物(如R407A、R407F和R442A)具較低的排放溫度。這允許它們被用於廣泛範圍的製冷應用中,在這些應用中具高排放溫度的冷媒與某些類型的壓縮機合用可引致問題。在固有設備中(其中壓縮機被設計為使用R404A和R507的)把R404A或R507取代時尤其如是。
雖然烴和二氧化碳(CO2
)在製冷系統中是技術上可用的,且兩者相比HFC皆具有低不少的GWP,但這些R404A和R507替代品具有其固有的缺點,其減低其通用性,特別是在如超市等公眾地方的通用性。高度可燃的烴只可在結合二級製冷迴路的情況下安全使用,這引致低能源效益和較高成本。CO2
在系統的高壓側必須以跨臨界狀態使用,這又是引致能源效益上的失利。該非常高的運作壓力(一般超過100巴表壓)呈現顯著的安全隱患。烴和CO2
皆不能被重配入固有的R404A和R507製冷機中。
根據本發明,一種冷媒摻合物包含
R125 20-35%
R32 20-35%
R1234ze(E) 25-50%
R227ea 1-10%
其中該些百分比是以重量計並選自所述的範圍以致合計為100%。
較佳的摻合物具有的直接GWP為低於1,500但高於1,000。較佳的摻合物亦符合ASHRAE標準34的要求而為非可燃的。
特別佳的摻合物具有的直接GWP處於的範圍為高於1000,較佳地高於1290,更佳地高於1270,最佳地高於1200,上限為1340。
在本發明的較佳實施方案中,摻合物本質上是由所列舉的HFC組成,以致任何附加的組份或雜質存在的份量也不足以影響該摻合物的本質屬性。
特別佳的實施方案由所列舉的成份組成,以致沒有任何額外的成份存在。
特別佳的冷媒具有的直接GWP為少於R404A和R507的直接GWP的一半,且某些實施例少於R404A和R507的直接GWP的三分一。
本發明的較佳實施方案提供冷媒,其本質上由非易燃的HFC125和HFC227ea以及易燃的HFC32和HFO-1234ze(E)的摻合物組成,其比例被選取以致該些摻合物在分餾期間為非易燃的,同時提供的製冷效果和性能和擬以其取代的冷媒(即R404A和R507)相比是類似或更優的。
HFO-1234ze(E)是反-1,3,3,3-四氟-1-丙烯。它於30°C以下是非易燃的,但於較高溫度下變成易燃。令人驚訝地,我們發現,將HFO-1234ze(E)與上至40%(重量)的非易燃的HFC-227ea混合,可產生本質上共蒸餾的摻合物,其根據ASHRAE 34標準於上至至少60°C的溫度下皆為非易燃的。這HFO-1234ze(E) / HFC-227ea摻合物可與HFC-32和HFC-125的非易燃的、本質上共蒸餾的摻合物混合,以提供全部四個組份的摻合物,其根據ASHRAE 34的標準為非易燃的,且在製冷裝置中可用以取代R404A和R507。
本發明提供的冷媒摻合物可與任何適用於HFC冷媒的潤滑劑合用,包括但不限於多元醇酯(POE),聚亞烷基乙二醇(PAG)以及兩者的摻合物。雖然已知HFC和HFO一般可與這些潤滑劑混溶,但於-30°C以下,特別是於-35°C以下的蒸發溫度下,蒸發器中的液體可分離成一較高黏度、高油份的相態和一較低黏度、高冷媒成份的相態。已發現較高的黏度會塗覆蒸發器的各內部表面,因而減低傳熱量並對能源效益構成不良影響。潤滑劑累積於蒸發器中,亦可引致壓縮機油槽中的份量減少,導致壓縮機過度磨損。不是期望受限於某理論,但這裏認為,在冷媒摻合物中R227ea的存在可有助將該兩液體相態乳化,以提供乳液,其可更易於被冷媒的流動驅動通過該蒸發器並返回壓縮機。
該些含氧的POE和PAG潤滑劑亦可與上至50%的烴類潤滑劑混合,其例如為礦物油,烷基苯和聚α-烯烴。
一種較佳的冷媒摻合物包含:
R125 22-33%
R32 22-33%
R1234ze(E) 30-45%
R227ea 2-9%
又一種較佳的冷媒摻合物包含:
R125 25-32%
R32 25-32%
R1234ze(E) 32-43%
R227ea 3-8%
另一種較佳的冷媒摻合物是:
R125 26-30%
R32 26-30%
R1234ze(E) 34-42%
R227ea 3-7%
另一種較佳的冷媒摻合物是:
R125 27-29%
R32 27-29%
R1234ze(E) 36-40%
R227ea 3-6%
另一種較佳的冷媒摻合物包含:
R125 28%
R32 28%
R1234ze(E) 39%
R227ea 5%
另一種較佳的冷媒摻合物包含:
R125 27%
R32 27%
R1234ze(E) 42%
R227ea 4%
另一種較佳的冷媒摻合物包含:
R125 27%
R32 27%
R1234ze(E) 43%
R227ea 3%
另一種較佳的冷媒摻合物包含:
R125 27%
R32 27%
R1234ze(E) 42%
R227ea 4%
另一種較佳的冷媒摻合物包含:
R125 27%
R32 27%
R1234ze(E) 41%
R227ea 5%
這摻合物具有的GWP少於1400但高於1100,而且是非易燃的。
另一種較佳的冷媒摻合物包含:
R125 27%
R32 27%
R1234ze(E) 38%
R227ea 8%
這摻合物具有的GWP少於1400但高於1100,而且是非易燃的。
另一種較佳的冷媒摻合物包含:
R125 26.5%
R32 26.5%
R1234ze(E) 41%
R227ea 6%
這摻合物具有的GWP少於1400但高於1100,而且是非易燃的。
本發明允許取代R404A和R507這兩種於較低溫度製冷設備中最常用的冷媒,以具1000和1600之間的GWP的摻合物提供約三分二的可觀GWP減額,且並不減低任何性能,包括能源效益和製冷量。
本發明進一步以實施例說明,但其並沒有限制性。
實施例1至實施例7
於表1中所示的、含有R32、R125、R-1234ze(e)及R227ea的摻合物的循環性能以NIST的Cycle D程式第4版於如表1所示的、典型的低溫、超市製冷環境中進行模擬。這些摻合物是商用的冷媒R404A(例1)和R507(例8)的取代品,它們的性能皆於表2中提供。
Claims (16)
- 一種冷媒摻合物,其只包含申請專利範圍第1至14項之任一項中所述的組份。
- 如申請專利範圍第15項所述的冷媒摻合物,其具有的全球變暖潛能大於1000。
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Application Number | Priority Date | Filing Date | Title |
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GBGB1505230.1A GB201505230D0 (en) | 2015-03-27 | 2015-03-27 | Non ozone depleting and low global warming refrigerant blends |
GB1505230.1 | 2015-03-27 | ||
GBGB1602586.8A GB201602586D0 (en) | 2015-03-27 | 2016-02-12 | Non ozone depleting and low global warming refrigerant blends |
GB1602586.8 | 2016-02-12 |
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TW201639943A TW201639943A (zh) | 2016-11-16 |
TWI686467B true TWI686467B (zh) | 2020-03-01 |
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US (1) | US10253233B2 (zh) |
EP (1) | EP3274415B1 (zh) |
CA (1) | CA2980969C (zh) |
CY (1) | CY1123004T1 (zh) |
DK (1) | DK3274415T3 (zh) |
ES (1) | ES2794609T3 (zh) |
GB (2) | GB201505230D0 (zh) |
PT (1) | PT3274415T (zh) |
TW (1) | TWI686467B (zh) |
WO (1) | WO2016156812A1 (zh) |
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MX2020005455A (es) * | 2017-11-27 | 2020-08-27 | Rpl Holdings Ltd | Mezclas refrigerantes de bajo pcg. |
EP4214292A2 (en) | 2020-10-22 | 2023-07-26 | RPL Holdings Limited | Thermal pump refrigerants |
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- 2016-03-23 DK DK16717988.6T patent/DK3274415T3/da active
- 2016-03-23 PT PT167179886T patent/PT3274415T/pt unknown
- 2016-03-23 EP EP16717988.6A patent/EP3274415B1/en active Active
- 2016-03-23 ES ES16717988T patent/ES2794609T3/es active Active
- 2016-03-23 US US15/558,540 patent/US10253233B2/en active Active
- 2016-03-23 CA CA2980969A patent/CA2980969C/en active Active
- 2016-03-23 WO PCT/GB2016/050827 patent/WO2016156812A1/en active Application Filing
- 2016-03-24 TW TW105109172A patent/TWI686467B/zh active
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2020
- 2020-05-25 CY CY20201100476T patent/CY1123004T1/el unknown
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US20180066171A1 (en) | 2018-03-08 |
DK3274415T3 (da) | 2020-06-02 |
WO2016156812A1 (en) | 2016-10-06 |
PT3274415T (pt) | 2020-06-02 |
GB201602586D0 (en) | 2016-03-30 |
US10253233B2 (en) | 2019-04-09 |
CY1123004T1 (el) | 2021-10-29 |
TW201639943A (zh) | 2016-11-16 |
EP3274415B1 (en) | 2020-03-18 |
CA2980969A1 (en) | 2016-10-06 |
CA2980969C (en) | 2020-01-14 |
EP3274415A1 (en) | 2018-01-31 |
GB201505230D0 (en) | 2015-05-13 |
ES2794609T3 (es) | 2020-11-18 |
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