CN105102579B - 1,3,3-三氯-1,1-二氟丙烷和氟化氢的共沸组合物 - Google Patents

1,3,3-三氯-1,1-二氟丙烷和氟化氢的共沸组合物 Download PDF

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CN105102579B
CN105102579B CN201480014684.9A CN201480014684A CN105102579B CN 105102579 B CN105102579 B CN 105102579B CN 201480014684 A CN201480014684 A CN 201480014684A CN 105102579 B CN105102579 B CN 105102579B
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D·C·默克尔
K·A·波克洛夫斯基
童雪松
汪海有
S·A·科特雷尔
H·T·范
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Abstract

提供1,3,3‑三氯‑1,1‑二氟丙烷(HCFO‑242fa)和氟化氢的共沸或类共沸混合物。此类组合物在HFC245fa和HCFO1233zd的生产中可作为原料或中间物使用。

Description

1,3,3-三氯-1,1-二氟丙烷和氟化氢的共沸组合物
技术领域
本发明涉及1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa)和氟化氢(HF)的共沸或类共沸组合物。
背景技术
基于氯氟烃(CFC)的化学品已经被广泛用于工业中多种不同的应用中,其中包括作为制冷剂、气溶胶抛射剂、发泡剂和溶剂。然而,某些CFC具有消耗地球的臭氧层的嫌疑。因此,已经引入了更为环境友好的替代品作为对CFC 的替代。例如,对于某些工业应用,诸如泡沫发泡剂和溶剂,1,1,1,3,3-五氟丙烷 (HFC-245fa)被认为具有有利的物理性质,并因此被视作以前用于这些应用的 CFC的良好的替代品。遗憾的是,目前认为在工业应用中某些氢氟烃包括 HFC-245fa的使用,对全球变暖具有影响。因此,现在正在寻找对于氢氟烃的更为环境友好的替代品。
化合物1-氯-3,3,3-三氟丙烯,还被称为HCFO-1233zd或简称为1233zd,在一些应用中(包括用作发泡剂和溶剂)是用于替代HFC-245fa的候选。1233zd 具有Z-异构体和E-异构体。由于这两种异构体之间物理性质的不同,纯1233zd (E)、纯1233zd(Z),或这两种异构体的特定混合物可适用于特定的应用例如制冷剂、抛射剂、发泡剂、溶剂或其他用途中。
1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa,或简称为242fa)可为245fa和1233zd 两者生产中的起始材料或中间物(若用较少氟化的氯烃例如HCC-240fa、1,1,3,3- 四氯丙烯、1,3,3,3-四氯丙烯、和/或1,1,3,3-四氯-1-氟丙烷开始反应),其为现有技术中公知的,如分别在美国专利5763706和6844475中所描述的。在1233zd 的情况下,参见美国专利公开第2011-0201853号。这些文件在此通过引用并入本文。
目前已经发现,在245fa和1233zd两者的生产中重要的原料或中间物是 1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa)和氟化氢(HF)的共沸或类共沸混合物。一旦形成该中间物,其后可将所述中间物通过萃取或蒸馏技术分离成组成部分。在标准大气压下,HCFO-242fa的沸点大约为109℃且HF的沸点大约为20℃。共沸或类共沸组合物不仅用作245fa和1233zd生产中的反应器进料,还另外可用作溶剂组合物以用于去除金属的表面氧化。
发明概述
本发明提供基本上由1,3,3-三氯-1,1-二氟丙烷(242fa)和氟化氢(HF)组成的非均相共沸组合物。
本发明进一步提供基本上由约90至约97重量%的氟化氢和约10至约3重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成的共沸或类共沸组合物,在约7.1psia 的压力下,组合物的沸点为约0℃。
本发明还提供形成非均相共沸或类共沸组合物的方法,所述组合物基本上由约1至约99重量%的氟化氢和约99至约1重量%的1,3,3-三氯-1,1-二氟丙烷 (242fa)共混组成,在约7.1psia至约17.9psia的压力下,组合物的沸点为约0 ℃至约25℃。
本发明还提供形成非均相共沸或类共沸组合物的方法,所述组合物基本上由约0.2至约97重量%的氟化氢和约99.8至约3重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)共混组成,在约7.1psia至约17.9psia的压力下,组合物的沸点为约 0℃至25℃。
与本发明相关的本领域技术人员应意识到,在此描述的关于本发明的任何特定方面和/或实施方案的任何特征可以与在此描述的本发明的任何其它方面和 /或实施方案的一种或多种任何其它特征相结合,并酌情修正以确保结合的相容性。这样的结合被视作是本公开所涉及的本发明的一部分。
将理解的是,前面的一般描述和接下来的详细描述仅仅是示例性和说明性的,而不是对要求保护的发明的限制。通过研究说明书和本发明在此公开的实践,其它实施方案将对于本领域技术人员而言得以明确。
附图简述
图1表示了在0℃测量下实施例1中形成的混合物的蒸气压的绘制图。
优选实施方案的详细描述
令人惊奇地,已经发现当将1,3,3-三氯-1,1-二氟丙烷(242fa)和HF进料至反应器中时,242fa与HF形成了共沸或类共沸混合物。在产品物流中发现了未反应的242fa/HF中间物。
通过流体的压力、温度、液体组成和蒸气组成来定义它的热力学状态。对于真正的共沸组合物,在给定的温度和压力下,液体组成和蒸气相是基本上相同的。在实践中这意味着组分在相变中无法分离。
就本发明而言,共沸物是液体混合物,相对于周围的混合物组分的沸点,其表现出最大或最小的沸点。共沸或类共沸组合物是两种或更多种不同组分的混合物,其在给定的压力下为液体形式时,将在一基本恒定的温度下沸腾,该温度可高于或低于组分的沸腾温度并且经历沸腾时将提供与液体组成基本上相同的蒸气组成。
就本发明而言,共沸组合物定义为包括类共沸组合物,其意味着表现类似于共沸物的组合物,即具有恒定沸腾特征或在沸腾或蒸发时不分馏的趋势。因此,在沸腾或蒸发过程中形成的蒸气组成与原始的液体组成相同或基本上相同。因此,在沸腾或蒸发过程中,若液体组成发生改变,则仅改变至极小或可忽略的程度。这与非类共沸组合物形成了对比,在非类共沸组合物中在沸腾或蒸发过程中,液体组成改变至实质性的程度。
因此,共沸或类共沸组合物的基本特征是:液体组合物在给定的压力下的沸点是固定的,并且在沸腾组合物之上的蒸气组成基本上是沸腾的液体组合物的组成,即基本上没有液体组合物组分的分馏发生。当共沸或类共沸液体组合物在不同的压力下经受沸腾时,共沸组合物的各个组分的沸点和重量百分比均可改变。
因此,共沸或类共沸组合物可以依据组分间存在的关系或依据组分的组成范围或依据在指定压力下以固定沸点为特征的组合物的各个组分的精确的重量百分比来定义。
本发明提供包含有效量的氟化氢和242fa以形成共沸或类共沸组合物的组合物。有效量意味着当与其他组分结合时,导致共沸或类共沸混合物的形成的每种组分的量。本发明的组合物优选为二元共沸物,其基本上仅由氟化氢和 242fa的结合组成。
在一个优选的实施方案中,本发明的组合物含有约99至约1重量%的HF,优选约95重量%至约5重量%并且最优选约85重量%至约15重量%。在另一个优选的实施方案中,本发明的组合物含有约1至约99重量%的242fa,优选约5重量%至约95重量%并且最优选约15重量%至约85重量%。
在约7.1psia的压力下,本发明的组合物具有大约为0℃的沸点。已经发现具有约89±2重量%的HF和约11±2重量%的242fa的共沸或类共沸组合物在约 0℃和7.1psia下沸腾。
下面的非限制性实施例用于举例说明本发明。
实施例1
12.2g的1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa)与13.2g的HF结合以形成非均相共沸混合物。该实验在0℃和7.1psia下完成(目测)。
实施例2
共混仅含有1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa)和HF的二元组合物以形成不同组成的非均相共沸混合物。在0℃下测量混合物的蒸气压并且注意到下面的结果。
表1显示了在约0℃的恒定温度下作为HF的重量百分比组成的函数的242fa 和HF的蒸气压的测量。
表1:242fa/HF的P-T-X,在T=0℃下
这些数据还显示混合物是共沸物,因为在所有示出的共混比例中,242fa和 HF的混合物的蒸气压都比单独的242fa和HF,即如第一行和最后一行所示,当HF为0.0wt%且242fa为100.0wt%以及当242fa为0.0wt%且HF为100.0wt%时的蒸气压更高。表1中的数据在图1中以图表形式显示。
实施例3
242fa/HF混合物的共沸组成还通过蒸气-液-液平衡(VLLE)实验来证明。 13.9g的1,3,3-三氯-1,1-二氟丙烷(HCFO-242fa)与13.7g的HF结合以形成0℃下的非均相混合物(目测)。在0℃温度和7.1psia的压力下取样混合物的蒸气组合物。结果表明共沸组成在0℃下大约为89±2wt%的HF。
在0℃温度和7.1psia压力下观察到该混合物为非均相共沸物。
在此所用的,除非上下文明确地另外说明,单数形式的“一个”、“一种”和“所述”包括复数形式。此外,当以上限优选值以及下限优选值的范围、优选范围,或列表的形式给出量、浓度,或其他值或参数时,将其理解为详细公开了所有范围,其由任意上限范围界限或优选值和任意下限范围界限或优选值的任意一对形成,不论范围是否单独公开。当在此叙述数值范围时,除非另有说明,该范围旨在包含其端点,以及该范围内的所有整数和分数。当限定范围时并不是要将本发明的范围限制于所叙述的指定值。
应当理解的是前面的描述仅仅是对本发明的举例说明。本领域技术人员可以在不脱离本发明的情况下设计各种替代方案和改进。因此,本发明旨在涵盖落入所附权利要求范围内的所有这样的替代方案、改进和变型。

Claims (6)

1.一种共沸或类共沸组合物,其由1重量%至86.2重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)和99重量%至13.8重量%的氟化氢组成,在7.1psia至17.9psia的压力下,组合物的沸点为0℃至25℃。
2.一种共沸或类共沸组合物,其由13.8重量%至97重量%的氟化氢和86.2重量%至3重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成,在7.1psia至17.9psia的压力下,组合物的沸点为0℃至25℃。
3.权利要求1的组合物,其由90重量%至97重量%的氟化氢和10重量%至3重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成,在7.1psia的压力下,组合物的沸点为0℃。
4.权利要求1的组合物,其由95重量%至13.8重量%的氟化氢和5重量%至86.2重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成。
5.权利要求1的组合物,其由85重量%至15重量%的氟化氢和15重量%至85重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成。
6.权利要求1的组合物,其由89±2重量%的氟化氢和11±2重量%的1,3,3-三氯-1,1-二氟丙烷(242fa)组成,在7.1psia的压力下,组合物的沸点为0℃。
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