CN1028032C - 氟代烃恒沸组合物 - Google Patents
氟代烃恒沸组合物 Download PDFInfo
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Abstract
五氟乙烷、二氟甲烷和四氟乙烷的三元混合物可用作制冷剂、喷雾推进剂、传热介质、气体电介质、灭火剂、聚烯烃和聚氨酯的膨胀剂和作为动力循环工作液。
Description
本申请是1990年12月17日递交的美国专利申请号07/628，000申请的部分继续。
本发明是关于一种恒沸混合物，该混合物可用作制冷剂、喷雾推进剂、传热介质、气体电介质、灭火剂、聚烯烃和聚氨基甲酸乙酯等聚合物的发泡剂或膨胀剂，以及动力循环工作液。具体地说，本发明是一种氟代烃的恒沸混合物。本发明还特别涉及到五氟乙烷（HFC-125）、二氟甲烷（HFC-32）和四氟乙烷（HFC-134和/或HFC-134a）混合物的应用。该混合物可以代替工业上大量应用的制冷剂502（R-502）、R-502是由氯代二氟甲烷（HCF-22）和氯代五氟乙烷（CFC-115）等组成的已在许多工业部门应用的二元共沸混合物。
近来，人们对氯代氯烃的长期环境效应作了大量细致的科学检验。认为这些含氯的材料在紫外线的辐照下在同温层中分解，释放出氯原子。人们推论氯原子在同温层与臭氧层发生化学反应，该反应消耗或至少减少同温层的臭氧层，从而使有害的紫外辐射穿过保护地球的臭氧层。同温层臭氧层的大量减少会对地球上的物种带来极为有害的影响。长期以来，致冷剂502、即约百分之47-50重量的HCFC-22和百分之53-50重量的CFC-115构成的共沸混合物（该共沸物的组成为百分之48.8重量的HCFC-22和百分之51.2重量的CFC-115）大多数国家中用作市售冷冻箱的制冷剂。然而，由于CFC-115是氯氟烃化合物，到2000年这类化合物将被逐步淘汰，这就要求在工业生产中用对环境无害的氟代烃取代制冷剂502。
有人已提出用四氟代乙烷（HFC-134和其异构体HFC-134a）作为可能的替代物，然而其低的蒸汽压（较高的沸点）限制了这些化合物单独使用时的制冷能力，不能很好地替代R-502。也有人建议用五氟代乙烷（HFC-125）代替R-502，但是，其能量效率（蒸发器带走的热量除以压缩蒸气所需的能量）比R-502低10%。结果，需要设计新的装置，以达到目前的这些市售用品所要求的制冷能力和能量效率。
如果用简单的混合物（不是恒沸的）能够获得这些所要求的性能，也可以使用对环境无害的材料的混合物。然而，简单的混合物对制冷系统的设备的设计和操作带来问题。这些问题主要产生于汽相和液相中组份的分离或隔离。
二组份或多组份的共沸或恒沸混合物看来能解决这一问题，该混合物的汽相和液相的组成在循环制冷过程中所经历的温度和压力的范围内是基本上相同的。
本发明的目的是提供至少由两种氢氟碳化合物组成的基本上恒沸的组合物，它是低沸点的，非可燃的，适合于用作制冷剂，喷雾式推进剂，传热介质，气体电介质，灭火剂，聚合物的膨胀剂或发泡剂，以及动力循环工作液。
本发明发现了一种三元氟代烃混合物，它包括约百分之5-90重量的五氟乙烷CF3-CHF2，也就是HFC-125，约百分之5-90重量的二氟甲烷，CH2F2，也就是HFC-32，和约百分之5-90重量的四氟乙烷，CF3-CH2F和CHF2-CHF2，也就是HFC-134a和HFC-134，它适合于上述用途，特别是用于市售的冷冻箱中。基本恒沸的组合物包括约5-59%重量的HFC-125，5-59%重量的HFC-32和约5-35%重量的HFC-134和HFC-134a中的至少一个。在任何情况下，HFC-134a的用量范围为约5-90%重量;如表2所示，在混合物中含15-70%重量的HFC-125和HFC-32是非常令人满意的。对于HFC-134，如表2所示，有量范围在约5-45%重量、最好15-45%重量之间是令人满意的。
本发明的组合物特别适合于制冷用途，因为如后面的实施例所示，在-30°F至115°F的温度和24psia至350psia的压力下，该组合物保持其稳定性和类共沸物特性。事实上，本发明的组合物可以在-50°F的低温至高达300°F的温度的范围内很好地使用。
本发明的新型的混合组合物呈现出不同的露点和沸点，然而，这些差别可以增加循环制冷体系的
整体能量效率，对于制冷设备的设计者来说是很有利的。
如表2所示，还有其它具有理想特性的三元和更多组份的共混物，本领域的技术人员可用所定义的卤化碳和本案的实例来配制。可配制的另一种适合于本发明目的的共混物是HFC-125/HFC-134a/HFC-134/HFC-32。
本说明书的目的不是为了鉴定每一种可能共混的成份，而是为了说明我们所发现的三元（或更多元）共混物能呈现出人意料的性能、这些性能取决于组份和所选定的比例。
在下面的讨论中，“近共沸的”意指基本上共沸的或基本上恒沸的。换句话说，这些术语的含意包括了近共沸性能的各种程度，它取决于各组份配比。正如本领域所公认的，有一系列的组合物，它们含有相同的组份。这些近共沸物在不同的温度和压力下表现出相同的性质，但是，却基本上呈现上述的性能。
这种新型的三元混合物可以用来产生制冷作用，方法是将该混合物压缩冷凝，随后，在要冷却的物体附近使该冷凝物蒸发。
这种新型混合物也可以用来产生热量，方法是将制冷剂在要加热的物体附近压缩冷凝，随后蒸发该制冷剂。
露点和沸点不同的非共沸混合物可以用于逆流热交换器，以发挥其潜在的能量效率的优势，这种性能是纯组份、共沸和近共沸混合物所不具有的。
与制冷剂502相比，新的混合物的臭氧消耗可能性（ODP）为零。ODP数据列于表1，用于比较。
新的混合物只有极小的地球变暖潜能，表1列出了混合物/组份的地球变暖潜能（GWP），其中R-502用于比较。（表1见文后）
也可以这样配制混合物，使其起始组合物或在泄漏期间的组合物保持为非可燃的。所谓“非可燃的”是指按照可燃性试验方法ASTM-E681-85，气体混合物在空气中遇点火器产生的火花时不会燃烧。
显然，表2所列的化合物的一种或多种可以用或与本发明的基本上恒沸的三元混合物替换或相结合，以便为相似的用途提供更多的基本上恒沸的混合物，同时只有添加了组分才使混合物增加有益的性能。
表2
名称 化学式
HFC-22 CHClF2
HFC-143a CH3CF3
HFC-161 CH2FCH3
FC-218 CF3CF2CF3
丙烷 CH3CH2CH3
HFC-23 CHF3
HFC-227ea CF3CHFCF3
通过参考下面的实施例，可以更清楚地理解本发明。
实施例1-12
表3列出了对本发明的新三元混合物制冷性能的评估，与制冷剂502比较。数据是以1吨计（one-ton basis），即在12.000BTU/hr速度下从某一空间转移的热量为基础。
“特性系数”（COP）是净制冷效能与压缩机作功之比，它是制冷剂能量效率的一种量度。
“净制冷效能”是蒸发器中制冷剂的焓的变化值，即蒸发器中的制冷剂转移的热量。
对于上述条件下的一类循环制冷体系，该混合物的COP或者比R-502高许多，或者两者基本上相同。这些混合物通过压缩器和蒸发器呈现出温度变化（入口温度与出口温度之差）。这些温度变化值为3至18°F不等，取决于混合物的组成。对于共沸的情况，温度变化值为0，对于近共沸混合物的情况，温度变化值可多达10°F。然而，这些温度变化不应对于设备制造者带来严重的问题。事实上，设计者利用大的温度变化来提高他们的机器的能量效率。而且，由于这类混合物有更高的蒸汽压，它们的容量比R-502大得多。
为了各种目的，本发明的新组合物中可以加入添加剂如润滑剂，腐蚀抑制剂，稳定剂，染料和其它适宜的材料，只要这些添加剂不会对组合物的应用带不良影响都可采用。
除制冷用途以外，本发明的新的恒沸组合物还可用作：喷雾状推进剂，传热介质、气体电介质、灭火剂、聚合物如聚烯烃和聚氨酯的膨胀剂，以及动力循环工作液。
实施例13
为了检验液态到汽态的相变过程中的分馏和蒸
汽压的变化，对五氟乙烷，四氟乙烷和二氟甲烷进行了相研究。
在75cc的不锈钢气缸中制备由五氟乙烷、1，1，1，2-四氟乙烷和二氟甲烷组成的共混物。该气缸配有磁搅拌器并浸于23.8℃的恒温浴中。用压力传感器连续地测量蒸汽压，在实验的不同阶段对蒸汽组合物取样并用标准的气相色谱法进行分析。起始和最终的液体浓度也用气相色谱分析。起始液体（IQ），最终液体（FQ），蒸汽组成和蒸汽压数据记录在表4，5和6中。（表4、5、6见文后）
这些数据（表4-6）表明，在起始加入量消耗了50%以上时，对于所有的情况，蒸汽压的变化小于16%。分馏的程度取决于四氟乙烷的浓度，并且可以调节这种分馏，使蒸汽压的变化很小。含有35wt%或更少的1，1，1，2-四氟乙烷（HFC-134a）的混合物被认为是基本上恒沸的，因为，在泄漏了50%的情况下，其蒸汽压的变化小于10%。含有35wt%以上的1，1，1，2-四氟乙烷的混合物被认为是非共沸的，因为，在泄漏了50%的情况下，其蒸汽压的变化小于10%。这些混合物对许多应用领域仍很有用，特别是那些要求非常小容量的应用。在小容量的情况中，可以补充由于蒸汽泄漏而减少的混合物，使其恢复到所需要的组成，作到这一点是不会有什么问题的。用1，1，2，2-四氟乙烷（HFC-134）取代HFC-134a，在较低浓度HFC-134的情况下，预计会得到相似的结果。
这些数据还表明，尽管该混合物分馏和蒸汽压降低，在泄漏过程中，液相和汽相中的二氟甲烷的浓度也都降低。因此，如果起始浓度的混合物是非可燃的，则该混合物也不会变成可燃的。可以预计，用HFC-134取代HFC-134a的混合物具有类似的性质。
实施例14
臭氧消耗潜能基于这样的比值，该比值通过计算得到的由发射一种化合物而导致的同温层臭氧的消耗量，与发射同样比例的CFC-11而导致的臭氧消耗潜能相比较所得，后者的臭氧消耗潜能被设定为1.0。在“一些卤化碳的破坏同温层臭氧的相对效率”（“The Relative Efficiency of a number of Halocarbons for Destroying Stratospheric Ozone”），D.J.Wuebbles，Lawrence Livermore Laboratory Report UCID-18924，1981，1月，和“氯烃发射状况：对同温层臭氧的潜在影响”（“Chlorocarbon Emission Scenarios：Potential Im-pact on Stratospheric Ozone”），D.J.Wuebbles，Jour-nal Geophysics Research，88，1433-1443，1983中叙述了计算臭氧消耗潜能的方法。
HFC-125（CF3CF2H），HFC-134a（CF3CFH2）或HFC-134（CF2HCF2H），和HFC-32（CF3H2）不含氯原子;因此，它们不具有臭氧消耗潜能（ODP＝0）。
用在联合国环境规划组主办的“同温层臭氧的科学评估：1989”（“Scientific Assessment of Stratospheric Ozone：1989”，Sponsored by the U.N.Environment Programme）中所述的方法确定氟代烃的地球变暖潜能（GWP）。GWP是发生于同温层的现象，可用模型来计算，该模型组合的参数是试剂在大气中的寿命及其红外横截面或其每摩尔红外吸收强度，可用红外分光光度计测量。
表1
制冷剂 化学式 ODP GWP
R-502 CHClF2/CClF2CF3.25 5.1
HFC-125 CHF2CF3.0 .65
HFC-134a CF3CH2F .0 .29
HFC-134 CHF2CHF2.0 .15
HFC-32 CH2F2.0 .15
表3
制冷性能对比
条件
蒸发器 凝结器
温度 温度
制冷剂 入口 出口 压力 入口 出口 压力 C.O.P. 净制冷 实施例
（°F） （°F） （psia） （°F） （°F） （psia） 效能
(BTU/1b)
R-502 -30 -30 -24.0 115 115 281.9 1.89 46.7 对比例
混合物
125/134a/32
（wt.%）
45/45/10 -34 -25 18.5 119 112 264.3 1.93 68.5 1
75/15/10 -32 -28 24.5 117 113 318.3 1.80 50.0 2
18/57/25 -36 -25 18.6 120 111 270.1 1.97 73.2 3
25/25/50 -34 -27 26.6 117 112 350.3 1.86 81.7 4
50/30/10 -34 -26 21.1 118 112 286.9 1.87 74.2 5
10/70/20 -36 -25 16.9 120 111 244.5 2.01 73.1 6
混合物
125/134/32
（wt.%）
45/45/10 -38 -23 16.5 121 109 250.1 1.95 61.7 7
75/15/10 -33 -27 24.0 117 113 315.7 1.80 50.8 8
18/57/25 -39 -21 16.0 123 108 240.7 2.01 77.9 9
25/25/50 -36 -25 24.5 119 111 337.9 1.87 84.2 10
50/30/10 -36 -25 19.7 119 111 281.7 1.87 56.1 11
10/70/20 -39 -21 13.6 123 108 216.8 2.07 78.8 12
表4
蒸汽压
组成（wt.%）
样品 损失的 HFC-125 HFC-134a HFC-32 （psia） （%变化）
百分数
IQ 0 48.2 17.3 33.9 207.2 0
1 6.3 51.0 4.2 44.6 206.0 0.6
2 12.5 51.8 7.1 41.1 204.0 1.2
3 18.8 50.9 8.6 40.5 203.6 1.7
4 25.0 50.9 9.5 39.7 202.2 2.4
5 31.3 50.6 10.7 38.7 200.5 3.2
6 37.5 50.6 11.2 38.1 198.5 4.2
7 43.8 50.6 12.0 37.5 196.5 5.2
8 50.4 50.6 12.2 37.2 193.7 6.5
FQ 50.4 49.4 22.0 28.6 193.7 6.5
表5
蒸汽压
组成（wt.%）
样品 损失的 HFC-125 HFC-134a HFC-32 （psia） （%变化）
百分数
IQ 0 33.9 38.2 27.9 188.4 0
1 8.3 41.2 18.8 39.5 104.1 2.3
2 16.7 40.9 21.9 37.3 180.8 4.0
3 25.0 40.2 24.0 35.7 178.3 5.4
4 33.0 38.9 25.3 35.0 174.0 7.6
5 41.8 37.4 30.3 32.3 171.2 9.1
6 51.0 37.3 32.5 30.2 168.7 10.4
FQ 51.0 30.2 47.0 22.7 168.7 10.4
表6
蒸汽压
组成（wt.%）
样品 损失的 HFC-125 HFC-134a HFC-32 （psia） （%变化）
百分数
IQ 0 18.7 56.4 24.8 173.2 0
1 1.7 26.5 36.9 36.6 172.1 0.4
2 6.2 25.5 37.5 37.0 169.7 1.4
3 10.6 25.3 38.5 36.2 164.5 2.4
4 15.1 24.8 40.2 35.5 162.5 3.5
5 19.6 24.2 41.6 34.3 160.1 4.5
6 24.4 24.4 40.9 34.6 158.4 5.7
7 28.9 23.8 42.8 31.3 155.6 7.1
8 33.3 22.8 45.9 31.3 154.0 8.4
9 37.8 23.1 45.7 31.2 151.3 9.8
10 42.2 23.4 46.3 31.6 149.0 11.2
11 46.7 20.8 49.7 29.5 146.3 12.8
12 48.9 21.1 51.8 27.4 144.1 13.8
13 54.4 21.4 51.3 27.3 140.2 15.8
FQ 54.4 12.7 73.1 14.2 140.2 15.8
Claims (1)
1、一种近共沸的基本上恒沸的混合物，该混合物包括大约5-59%重量的五氟乙烷，大约5-59%重量的二氟甲烷和大约5-35%重量的至少一种四氟乙烷，其中当混合物蒸发了50%重量时，其蒸汽压的变化小于10%。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62800090A | 1990-12-17 | 1990-12-17 | |
| US628,000 | 1990-12-17 | ||
| US07/649,356 US5185094A (en) | 1990-12-17 | 1991-02-01 | Constant boiling compositions of pentafluoroethane, difluoromethane, and tetrafluoroethane |
| US649,356 | 1991-02-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063300A CN1063300A (zh) | 1992-08-05 |
| CN1028032C true CN1028032C (zh) | 1995-03-29 |
Family
ID=27090590
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91112767A Expired - Lifetime CN1028032C (zh) | 1990-12-17 | 1991-12-11 | 氟代烃恒沸组合物 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5185094A (zh) |
| EP (1) | EP0563220B1 (zh) |
| JP (1) | JP2732545B2 (zh) |
| KR (1) | KR100208112B1 (zh) |
| CN (1) | CN1028032C (zh) |
| AT (1) | ATE124440T1 (zh) |
| AU (2) | AU9143391A (zh) |
| BR (1) | BR9107225A (zh) |
| CA (1) | CA2098610C (zh) |
| DE (1) | DE69110905T2 (zh) |
| DK (1) | DK0563220T3 (zh) |
| ES (1) | ES2074354T3 (zh) |
| GR (1) | GR3017006T3 (zh) |
| HK (1) | HK54397A (zh) |
| MX (1) | MX9102622A (zh) |
| MY (1) | MY116821A (zh) |
| WO (1) | WO1992011339A1 (zh) |
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- 1991-02-01 US US07/649,356 patent/US5185094A/en not_active Expired - Lifetime
- 1991-12-11 CN CN91112767A patent/CN1028032C/zh not_active Expired - Lifetime
- 1991-12-12 BR BR9107225A patent/BR9107225A/pt not_active IP Right Cessation
- 1991-12-12 KR KR1019930701818A patent/KR100208112B1/ko not_active Ceased
- 1991-12-12 DK DK92902204.4T patent/DK0563220T3/da active
- 1991-12-12 EP EP92902204A patent/EP0563220B1/en not_active Expired - Lifetime
- 1991-12-12 DE DE69110905T patent/DE69110905T2/de not_active Expired - Lifetime
- 1991-12-12 JP JP4502713A patent/JP2732545B2/ja not_active Expired - Lifetime
- 1991-12-12 AU AU91433/91A patent/AU9143391A/en not_active Abandoned
- 1991-12-12 CA CA002098610A patent/CA2098610C/en not_active Expired - Lifetime
- 1991-12-12 AT AT92902204T patent/ATE124440T1/de not_active IP Right Cessation
- 1991-12-12 WO PCT/US1991/009150 patent/WO1992011339A1/en not_active Ceased
- 1991-12-12 ES ES92902204T patent/ES2074354T3/es not_active Expired - Lifetime
- 1991-12-13 MY MYPI91002308A patent/MY116821A/en unknown
- 1991-12-17 MX MX9102622A patent/MX9102622A/es unknown
-
1995
- 1995-08-02 GR GR950402126T patent/GR3017006T3/el unknown
- 1995-10-06 AU AU33129/95A patent/AU686433B2/en not_active Expired
-
1997
- 1997-04-24 HK HK54397A patent/HK54397A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| US5185094A (en) | 1993-02-09 |
| KR100208112B1 (ko) | 1999-07-15 |
| DE69110905D1 (de) | 1995-08-03 |
| MY116821A (en) | 2004-03-31 |
| AU9143391A (en) | 1992-07-22 |
| EP0563220B1 (en) | 1995-06-28 |
| BR9107225A (pt) | 1994-04-05 |
| EP0563220A1 (en) | 1993-10-06 |
| AU686433B2 (en) | 1998-02-05 |
| JPH06503828A (ja) | 1994-04-28 |
| CN1063300A (zh) | 1992-08-05 |
| DK0563220T3 (da) | 1995-08-28 |
| GR3017006T3 (en) | 1995-11-30 |
| KR930703413A (ko) | 1993-11-30 |
| DE69110905T2 (de) | 1996-02-29 |
| CA2098610C (en) | 2004-04-06 |
| AU3312995A (en) | 1996-02-29 |
| ATE124440T1 (de) | 1995-07-15 |
| JP2732545B2 (ja) | 1998-03-30 |
| ES2074354T3 (es) | 1995-09-01 |
| MX9102622A (es) | 1992-06-01 |
| WO1992011339A1 (en) | 1992-07-09 |
| CA2098610A1 (en) | 1992-06-18 |
| HK54397A (en) | 1997-05-02 |
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| C14 | Grant of patent or utility model | ||
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| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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Expiration termination date: 20111211 Granted publication date: 19950329 |