TWI625321B - 以1,3,3,3-四氟丙烯為基礎之組成物 - Google Patents
以1,3,3,3-四氟丙烯為基礎之組成物 Download PDFInfo
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Abstract
本發明的主題為一種包含以多元醇酯(POE)或PVE為基礎之潤滑劑及包含從1至99重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從1至99重量%之1,1,1,2-四氟乙烷的冷凍劑F之組成物。本發明的主題亦為該組成物在冷凍、空氣調節及熱泵中之用途。
Description
本發明關於一種含有反-1,3,3,3-四氟丙烯和1,1,1,2-四氟乙烷及至少一種潤滑劑之組成物,該組成物能夠用於冷凍、空氣調節及熱泵中。
在蒙特婁(Montreal)處理由耗盡大氣臭氧層之物質所呈現的問題,在此簽署強制減少氯氟碳類(CFC)之製造及使用的議定書。此議定書已成為要求放棄CFC且延伸條款至其他產品(包括氫氯氟碳類(HCFC))的修正議案之主題。
冷凍及空氣調節工業已大量投資在該等冷凍劑的替換,且因為此替換而於市場上銷售氫氟碳類(HFC)。
在機動車輛產業中,許多國家所販售之車輛的空氣調節系統已從氯氟碳(CFC-12)冷凍劑改變成較不傷害臭氧層的氫氟碳(1,1,1,2-四氟乙烷:HFC-134a)冷凍劑。然而,從京都(Kyoto)議定書所設定之目標觀點而言,HFC-134a(GWP=1430)被視為具有高發熱功率。冷凍劑對溫室效應的貢獻程度係經標準GWP(全球暖化潛能)量化,該GWP概述的發熱功率係以二氧化碳的參考值為1所表示的。
氫氟烯烴(HFO)具有低的發熱功率且因此符合京都議定書所設定之目標。文件JP 4-110388揭示氫氟丙烯作為
熱轉移劑。
在工業部門中,最常使用的冷凍機係以藉由蒸發液體冷凍劑而冷卻為基礎。在蒸發之後,將冷凍劑壓縮及接著冷卻,以恢復成液態及因此繼續循環。
所使用之冷凍壓縮機具有往復式、渦捲、離心或螺旋類型。壓縮機的內部潤滑通常不可或缺,以減少移動組件的磨損和發熱、實現壓縮機的滲漏緊度及防護壓縮機免於腐蝕。
除了滿意的熱轉移劑性質以外,為了於商業上接受冷凍劑,其必須特別顯出熱穩定性及與潤滑劑的相容性。尤其非常希望冷凍劑與在壓縮機中所使用而存在於大多數冷凍系統中的潤滑劑相容。冷凍劑與潤滑劑的此組合對冷凍系統的實施及效率具有重要性;潤滑劑特別於整個操作溫度範圍內應充分可溶於或混溶於冷凍劑中。
因此,聚伸烷二醇類(PAG)已發展為機動車輛空氣調節中的HFC-134a之潤滑劑。
1,1,3,3,3-五氟丙烯及1,3,3,3-四氟丙烯與潤滑劑的混溶性試驗已說明於文件WO 2004/037913之實例2中。與聚伸烷二醇的相容性亦說明於實例3中。然而,該等試驗未指明1,3,3,3-四氟丙烯異構物之本質。
而且,文件WO 2005/108522揭示反-1,3,3,3-四氟丙烯及1,1,1,2-四氟乙烷的共沸組成物。
最近,2,3,3,3-四氟丙烯被選為冷凍劑,以替換機動車輛空氣調節中的HFC-134a。
申請者現發展出可用於冷凍、空氣調節及熱泵中的冷凍劑與潤滑劑配對。
本發明的主題因此為一種組成物,其包含至少一種以多元醇酯(POE)或以聚乙烯醚(PVE)為基礎之潤滑劑及包含從1至99重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從1至99重量%之1,1,1,2-四氟乙烷的冷凍劑F。
根據本發明的組成物較佳地包含至少一種以多元醇酯(POE)或聚乙烯醚(PVE)為基礎之潤滑劑及包含從5至95重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從5至95重量%之1,1,1,2-四氟乙烷的冷凍劑F。
特別佳的組成物包含至少一種以多元醇酯(POE)或以聚乙烯醚(PVE)為基礎之潤滑劑及包含從30至91重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從9至70重量%之1,1,1,2-四氟乙烷的冷凍劑F。
冷凍劑F亦可包含其他的氫氟碳類。
流體F具有比反-HFO-1234ze更有效的優點,而另外,在POE或PVE存在下的冷凍劑穩定性與在PAG存在下的反-HFO-1234ze的穩定性相比而更大。
多元醇酯係藉由將多元醇(含有至少2個羥基-OH之醇)與單官能性或多官能性羧酸或與單官能性羧酸之混合物反應而獲得。除去在此反應期間所形成的水以避免逆反應(亦即水解)。
根據本發明,較佳的多元醇為那些具有新戊基骨架的多元醇,諸如新戊基乙二醇、三羥甲基丙烷、季戊四醇及二季戊四醇,季戊四醇為較佳的多元醇。
羧酸可含有從2至15個碳原子,碳骨架可能為直鏈或支鏈。可特別述及為正戊酸、正己酸、正庚酸、正辛酸、2-乙基己酸、2,2-二甲基戊酸、3,5,5-三甲基己酸、己二酸及丁二酸和其混合物。
一些醇官能未經酯化,然而其仍是低比例。因此,POE可包含相對於-CH2-O-(C=O)-單元的0與5相對莫耳%之間的CH2-OH單元。
較佳的POE潤滑劑為那些在40℃下具有從1至1000厘史(centiStokes)(cSt)之黏度,較佳從10至200cSt,而最好從30至80cSt。
聚乙烯醚(PVE)油較佳為下列2種單元之共聚物:
油的性質(特別為黏度、冷凍劑的溶解度及與冷凍劑的混溶性)可藉由改變m/n之比及m+n之總和來調整。較佳的PVE油為那些具有50至95重量%之單元1的油。
根據本發明的一個較佳的具體例,潤滑劑佔該組成物重量的10與50%(含)之間。
冷凍劑F亦可包含添加劑,諸如氣味化合物。
本發明的主題亦為上述組成物於下列之用途:冷凍,特別為家庭或商業用冷凍、冷室、食品工業、加工工業、冷凍運輸(卡車、輪船);空氣調節,特別為家庭、商業或工業用空氣調節,在此所使用的器具為冷卻機或直膨式器具;及熱泵,特別為中-及高溫熱泵。
由於根據本發明的組成物之低滑落溫度而使其可用於具有乾膨脹式蒸發器之設備及具有在浸沒式系統中操作的蒸發器之設備二者中。
熱穩定性試驗係根據標準的ASHRAE 97-2007:〝用於測試在冷凍系統內使用的材料之化學穩定性的密封式玻璃管方法〞進行。
試驗條件如下:
冷凍劑重量:2.2公克
潤滑劑重量:5公克
溫度:200℃
期間:14天
將潤滑劑引入42.2毫升玻璃管中。接著將玻璃管在真空下抽空及接著將冷凍劑F添加至其中。接著將玻璃管熔接,使其封閉且放入200℃之烘箱中14天。
在試驗結束時進行各種分析:
-將氣相回收,以氣相層析術分析:主要雜質係以GC/MS(氣相層析術與質譜法結合)鑑證。來自冷凍劑F及那些來自潤滑劑的雜質因此可組合;
-分析潤滑劑:色彩(以分光光度計,Labomat DR Lange LICO220型MLG131)、水含量(以Karl Fischer電量滴定法,Mettler DL37)及酸值(以0.01N甲醇氫氧化鉀的定量測定)。
以3種市售潤滑劑測試:PAG ND8油、POE Ze-GLES RB68油及PVE FVC 68D油。
應注意在POE或PVE的存在下以反-HFO-1234ze改進潤滑劑的穩定性。另外,在POE的存在下亦改進冷凍劑的穩定性。
使用RK-Soave公式計算混合物的密度、焓、熵及液體-蒸氣平衡數據。此公式的使用需要了解在討論中的混合物中所使用之純物質的性質及亦了解各二元組合的交互作用係數。
沸點、臨界壓力和溫度、以從沸點開始至臨界點的溫度為函數之壓力曲線、以溫度為函數之飽和液體和飽和蒸氣密度。
HFC的數據發表於ASHRAE Handbook 2005 chapter 20中且亦可以Refrop取得(由NIST所發展用於計算冷凍劑性質的軟體)。
HFO溫度-壓力曲線數據係以靜態方法測量。臨界壓力和溫度係使用由Setaram所販售之C80量熱計測量。以溫度為函數在飽和時的密度係利用由the cole des Mines de Paris[法國工程學校(French Engineering School)]實驗室所發展之振動管密度計技術來測量。
RK-Soave公式使用二元交互作用係數代表在混合物中的產物行為。該係數係根據實驗的液體-蒸氣平衡數據來計算。
用於液體-蒸氣平衡測量的技術為靜態分析分格法。平衡分格包含藍寶石管且配備有兩個Rolsitm電磁取樣器。將其插入低溫恆溫(cryothermostat)浴(Huber HS40)中。使用在不同速度下旋轉的磁場驅動之磁攪拌加速達到平衡。樣品分析係藉由使用導熱氣體分析儀(katharometer)(TCD)的氣相層析術(HP5890系列II)來進行。
對HFC-134a/反-HFO-1234ze二元組合的液體-蒸氣平衡測量係就以下的恆溫法進行:20℃。
考慮配備有蒸發器、冷凝器、液體-蒸氣交換器(內部交換器)、螺旋式壓縮機及壓力調節劑之壓縮系統。
該系統係以過熱15℃及在冷凝器出口與蒸發器出口之間的內部交換器操作。
壓縮機的等熵效率係取決於壓縮比而定。此效率係根據以下公式計算:
就螺旋式壓縮機而言,等熵效率公式(1)的常數a、b、c、d及e係根據在〝Handbook of air conditioning and refrigeration,page 11.52〞中所發表之標準數據計算。
效能係數(COP)係經定義為由系統供給之有用功率對由系統引入或消耗之功率。
Lorenz效能係數(COPLorenz)為參考用效能係數。其係取決於溫度而定,且使用該係數與各種冷凍劑的COP比較。
Lorenz效能係數係經定義如下:
(溫度T係以K計)
在經調節之空氣及冷凍劑的例子中之Lorenz COP:
在發熱的例子中之Lorenz COP:
就各組成物的Lorenz循環之效能係數係以對應之溫度為函數而計算。
%COP/COPLorenz為系統的COP相對於對應之Lorenz循環的COP之比。
在冷卻模式中,壓縮系統係在介於-5℃之蒸發溫度與50℃之冷凝溫度之間操作。
各組成物之成分值(HFC-134a,反-HFO-1234ze)係以重量百分比提出。
在發熱模式中,壓縮系統係在介於-5℃之蒸發溫度與50℃之冷凝溫度之間操作。
各組成物之成分值(HFO-134a,反-HFO-1234ze)係以重量百分比提出。
Claims (6)
- 一種組成物,其包含至少一種以多元醇酯(POE)為基礎之潤滑劑及包含從5至95重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從5至95重量%之1,1,1,2-四氟乙烷的冷凍劑F;其中該POE係從具有新戊基骨架的多元醇獲得。
- 根據申請專利範圍第1項之組成物,其中該冷凍劑F包含從30至91重量%之反-1,3,3,3-四氟丙烯(反-HFO-1234ze)和從9至70重量%之1,1,1,2-四氟乙烷。
- 根據申請專利範圍第1項之組成物,其中該多元醇為新戊基乙二醇、三羥甲基丙烷、季戊四醇或二季戊四醇。
- 根據申請專利範圍第1項之組成物,其中該POE係從含有從2至15個碳原子之直鏈或支鏈羧酸獲得。
- 根據申請專利範圍第1項之組成物,其中該POE佔該組成物重量的10與50%之間。
- 一種根據申請專利範圍第1至5項中任一項之組成物在冷凍、空氣調節及熱泵中之用途。
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FR1057483A FR2964976B1 (fr) | 2010-09-20 | 2010-09-20 | Composition a base de 1,3,3,3-tetrafluoropropene |
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TW107101568A TWI654289B (zh) | 2010-09-20 | 2011-08-25 | 以1,3,3,3-四氟丙烯為基礎之組成物 |
TW100130504A TWI625321B (zh) | 2010-09-20 | 2011-08-25 | 以1,3,3,3-四氟丙烯為基礎之組成物 |
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EP (2) | EP2431442B1 (zh) |
JP (4) | JP2012062469A (zh) |
KR (1) | KR20120030948A (zh) |
CN (2) | CN106010454B (zh) |
AU (1) | AU2011224133B2 (zh) |
CA (1) | CA2749095C (zh) |
ES (1) | ES2676871T3 (zh) |
FR (1) | FR2964976B1 (zh) |
PL (1) | PL2431442T3 (zh) |
PT (1) | PT2431442T (zh) |
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