TW201842149A - 建基於氫氟烯烴類之組成物 - Google Patents

建基於氫氟烯烴類之組成物 Download PDF

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TW201842149A
TW201842149A TW107103873A TW107103873A TW201842149A TW 201842149 A TW201842149 A TW 201842149A TW 107103873 A TW107103873 A TW 107103873A TW 107103873 A TW107103873 A TW 107103873A TW 201842149 A TW201842149 A TW 201842149A
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威森 羅奇德
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法商艾克瑪公司
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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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
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    • 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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Abstract

本發明係關於包括氫氟烯烴之組成物及其作為傳熱液、發泡劑、溶劑和氣溶膠之使用。本發明之更特別的標的係包含5至65重量%(以5至15重量%為佳)的2,3,3,3-四氟丙烯，5至70重量%(以40至60重量%為佳)的HFC-134a和25至42重量%的HFC-32之組成物。

Description

建基於氫氟烯烴類之組成物
本發明係關於包括氫氟烯烴之組成物及其作為傳熱液、發泡劑、溶劑和氣溶膠之用途。
於蒙特婁處理消耗大氣臭氧層的物質(ODP：臭氧消耗潛質)所引發的問題，於蒙特婁簽訂的協定書要求減少氯氟化碳(CFC)之製造和使用。此協定書已構成修正案標的，該修正案要求不再使用CFC及以更多規則控管其他產品，包括氫氯氟化碳(HCFC)。
冷凍工業和空調產製已針對這些冷凍劑的替代品進行許多研究且因此氫氟化碳(HFC)上市。
亦曾使用(氫)氯氟化碳代替HFC作為發泡劑或溶劑。
在電動載具工業中，許多國家銷售的載具之空調系統自氯氟化碳(CFC-12)冷凍劑改為對臭氧層較無害的氫氟化碳(1,1,1,2-四氟乙烷：HFC-134a)冷凍劑。但是，由京都協定書設定的目標觀點，HFC-134a(GWP=1300)被 認為具有高加熱力。冷凍劑對溫室效應的影響藉規範(GWP(地球暖化潛能)，其為加熱力的指標，以二氧化碳作為參考值1)定出。
二氧化碳由於無毒且非可燃並具有極低的GWP，所以曾被建議作為供空調系統之用的冷凍劑以代替HFC-134a。然而，使用二氧化碳有數個缺點，特別關於其在現有裝置中作為冷卻劑的使用壓力極高和技術。
論文WO 2004/037913揭示包含至少一具有三或四個碳原子的氟烯(特別是五氟丙烯和四氟丙烯，以GWP至多150者為佳)之組成物作為傳熱液之使用。
論文WO 2005/105947指出輔助發泡劑(如，二氟甲烷、五氟乙烷、四氟乙烷、二氟乙烷、七氟丙烷、六氟丙烷、五氟丙烷、五氟丁烷、水和二氧化碳)添加至四氟丙烯(以1,3,3,3-四氟丙烯為佳)。
論文WO 2006/094303揭示2,3,3,3-四氟丙烯(1234yf)與二氟甲烷(HFC-32)和2,3,3,3-四氟丙烯與1,1,1,2-四氟乙烷(HFC-134a)的二元組成物。
該論文中亦揭示包含1,1,1,2,3-五氟丙烯(1225ye)與二氟甲烷、2,3,3,3-四氟丙烯和HFC-134a併用之四元混合物。但1,1,1,2,3-五氟丙烯具毒性。
亦於論文WO 2006/094303中揭示包含2,3,3,3-四氟丙烯與碘三氟甲烷(CF3I)、HFC-32和HFC-134a併用的四元混合物。但是，CF3I的ODP非0且有安定性和腐蝕方面的問題。
申請人的公司現已發展包括氫氟丙烯的組成物，該組成物不具前述缺點且兼具零ODP和比現有的傳熱液(如，R404A(五氟乙烷(44重量%)、三氟乙烷(52重量%)和HFC-134a(4重量%)的三元混合物)及R407C(HFC-134a(52重量%)、HFC-125(25重量%)和HFC-32(23重量%)的三元混合物))為低的GWP。
根據本發明之組成物之特徵在於其包含5至65重量%(以5至15重量%為佳)的2,3,3,3-四氟丙烯，5至70重量%(以40至60重量%為佳)的HFC-134a和25至42重量%的HFC-32。
根據本發明之較佳形式，該組成物包含25至42重量%的HFC-32、30至55重量%的2,3,3,3-四氟丙烯和20至35重量%的HFC-134a。
包含40重量%的HFC-32、10重量%的2,3,3,3-四氟丙烯和50重量%的HFC-134a之組成物係特別有利。
包含40重量%的HFC-32、40重量%的2,3,3,3-四氟丙烯和20重量%的HFC-134a之組成物亦有利。
有利地，根據本發明之組成物實質上包含2,3,3,3-四氟丙烯、HFC-134a和HFC-32作為氫氟碳(飽和或不飽和)。
根據本發明之組成物可作為傳熱液，在壓縮系統中較佳。它們特別適合用於冷凍，以作為R404A和HCFC-22 (氯二氟甲烷)的替代品為佳。
根據本發明之組成物亦適用於供空調和加熱用的壓縮系統，特別是熱幫浦，以作為R407C和HFC-134a的替代品為佳。
根據本發明之組成物可包含供2,3,3,3-四氟丙烯用的安定劑。相對於總組成物，該安定劑至多5重量%。
特別可提及作為安定劑者為硝基甲烷、抗壞血酸、對酞酸、唑(如，甲苯並三唑或苯並三唑)、酚系化合物(如，生育酚、氫醌、三級丁基氫醌或2,6-二(三級丁基)-4-甲酚)、環氧化物(烷基，隨意地經氟化或全氟化，或烯基或芳族)(如，正丁基縮水甘油醚、己二醇二縮水甘油醚、烯丙基縮水甘油醚或丁基苯基縮水甘油醚)、亞磷酸鹽、磷酸鹽、膦酸鹽或硫醇和內酯。
根據本發明之組成物可包含潤滑劑，如，礦油、烷基苯、聚烷二醇和聚乙烯醚。
根據本發明之組成物可同時作為發泡劑、氣溶膠和溶劑。
實驗部分
根據本發明之組成物在冷凍方面的效能示於表1。每一組成物的組成(1234yf/32/134a)值以重量%表示。
當涉及到以現有設備代替時，測定參數(如，效能係數(COP)、體積容量(容量)和高壓(Cond P)。就 R404A而言，在下列操作條件下，公稱操作壓力為1829kPa，容量為1471千焦耳/立方米，而COP為1.8：
蒸發溫度：-20℃
凝結溫度：40℃
壓縮機入口溫度：-5℃
次冷卻液體的溫度：35℃
壓縮機的等熵效率：70%
Evap P：蒸發器壓力
Cond P：凝結器壓力
Ratio：壓縮比
T comp outlet：壓縮機出口處溫度
COP：效能係數並在涉及冷凍時，定義為系統供應之有用的冷卻功率對系統引入或消耗的功率之比。
在與R404A相同的操作條件下，根據本發明之組成物之體積容量和COP等同或甚至高於自R404A得到的值。
根據本發明之組成物在空調和熱幫浦操作條件下之效能示於表2。每一組成物的組成值(1234yf/32/134a)以重量%表示。
就R407C而言，在下列操作條件下，公稱操作壓力為3442kPa，容量為1461千焦耳/立方米，而COP為2.1：
蒸發溫度：-5℃
凝結溫度：70℃
壓縮機入口溫度：5℃
次冷卻液體溫度：65℃
壓縮機的等熵效能：70%
Evap P：蒸發器壓力
Cond P：凝結器壓力
Ratio：壓縮比
T comp outlet：壓縮機出口處溫度
COP：效能係數並在涉及冷凍時，定義為系統供應之有用的冷卻功率與系統引入或消耗的功率之比。
在相同條件下，根據本發明之組成物提供的容量大於R407C的容量且可能使得使用尺寸較小的設備，減少冷凍劑用量及降低設備成本。

Claims (6)

  1. 一種組成物，其包含5至65重量%的2,3,3,3-四氟丙烯，5至70重量%的1,1,1,2-四氟乙烷HFC-134a和25至42重量%的二氟甲烷HFC-32，作為在冷凍中、在供空調和加熱用的壓縮系統中之傳熱液。
  2. 如申請專利範圍第1項之組成物，其中，其包含25至42重量%的HFC-32、30至55重量%的2,3,3,3-四氟丙烯和20至35重量%的HFC-134a。
  3. 如申請專利範圍第1項之組成物，其中，其包含40重量%的HFC-32、10重量%的2,3,3,3-四氟丙烯和50重量%的HFC-134a。
  4. 如申請專利範圍第1或2項之組成物，其中，其包含40重量%的HFC-32、40重量%的2,3,3,3-四氟丙烯和20重量%的HFC-134a。
  5. 如申請專利範圍第1項之組成物，其中，其包含5至15重量%的2,3,3,3-四氟丙烯、40至60重量%的HFC-134a和25至42重量%的HFC-32。
  6. 如申請專利範圍第1項之組成物，其代替五氟乙烷(44重量%)、三氟乙烷(52重量%)和HFC-134a(4重量%)的三元混合物R404A和氯二氟甲烷HCFC-22。
TW107103873A 2008-06-11 2009-05-21 建基於氫氟烯烴類之組成物 TWI688648B (zh)

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FR0853859A FR2932492B1 (fr) 2008-06-11 2008-06-11 Compositions a base d'hydrofluoroolefines

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US8252198B2 (en) 2012-08-28
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