CN107841290A - 适用于固定或移动空调系统的R‑744和R‑1234yf的制冷剂混合物 - Google Patents

适用于固定或移动空调系统的R‑744和R‑1234yf的制冷剂混合物 Download PDF

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CN107841290A
CN107841290A CN201710828176.XA CN201710828176A CN107841290A CN 107841290 A CN107841290 A CN 107841290A CN 201710828176 A CN201710828176 A CN 201710828176A CN 107841290 A CN107841290 A CN 107841290A
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refrigerant composition
ian robert
august eugene
lund ian
earl august
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爱德华·斯坦利·萨科维奇
安吉洛·帕蒂
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Abstract

公开了一种R‑1234yf和R‑744的制冷剂组合物。在一些实施例中，R‑744是按重量计组合物的5％或更少。在PVE用作润滑剂与制冷剂一起的示例中，R‑744可以是组合物的50％或更少。使用制冷剂的系统和使用该系统的方法也被公开。

Description

适用于固定或移动空调系统的R-744和R-1234yf的制冷剂混 合物
技术领域
本发明大体上涉及用于冷却系统——例如，空调和热泵——中传热的制冷剂组合物,并且更具体地，涉及适用于使用PAG、POE或PVE润滑油的固定或移动空调系统的R-744和R-1234yf的制冷剂混合物。
背景技术
关于制冷剂的环境影响的问题促使人们对功能相当但影响较低的替代品进行研究。制冷剂在传热系统中通过在低压下从液态蒸发而起作用，这需要周围的热能。在这样的系统中，蒸发的制冷剂被压缩并且从第一区域移动以提取该区域中的热并且之后冷凝返回至第二区域中的液态，在第二区域中其也释放热能。液体制冷剂可通过系统再循环并且有效地传递热至第二区域。对于制冷剂的功效选择，在于它能在这样的系统中发挥多大的作用。
在过去依赖的制冷剂已经显示它们对环境有害，导致行业调整关于制冷剂的臭氧破坏潜能值和全球变暖潜能值的标准。进一步地，一些制冷剂化合物挥发性强且易燃，使它们不适合消费者使用。因此，对确定制冷剂是安全的、有效的和达到行业标准有一种持续的需求。
发明内容
根据在此描述的目的和优点，本发明涉及使用与在汽油、柴油、混合动力或电动车辆中使用的压缩泵各种技术相容的单一或混合的润滑油混合的不易燃制冷剂的能力。
制冷剂组合物包含至少95％的R-1234yf和5％或更少的R-744。在一些实施例中，制冷剂组合物本质上由至少95％的R-1234yf和5％或更少的R-744组成。在其它实施例中，R-1234yf可至少构成组合物的96、97、98、99或99.5％。R-744可构成组合物的0.5、1、2、3、4或5％。
在其它方面中，制冷剂和润滑剂可构成用于空调单元的组合物。润滑剂可从由聚亚烷基二醇、聚乙烯基醚和多元醇酯油组成的组中选择。这样的组合物可用在传热装置中。
本发明进一步提供用于通过操作空间内的传热装置冷却空间的方法，其中传热装置使用新的和改进的制冷剂以从空间传递热。
在其它实施例中，具有聚乙烯基醚的制冷剂允许多达50％的R-744。本发明因此提供了一种用于空调单元的组合物，其包含PVE(聚乙烯基乙醚)和包含R-1234yf和大约50％或更少的R-744的制冷剂组合物。这样的制冷剂组合物可本质上由R-744和R-1234yf组成。
具体实施方式
制冷剂识别主要集中在识别单一化合物。本发明已经识别一种制冷剂组合物，其混合有制冷剂化合物，以致最终产物将有效冷却的需求与消费者安全和环境影响相平衡。
制冷剂组合物包含R-1234yf和R-744的混合物。制冷剂R-1234yf(2,3,3,3-四氟丙烯)是具有4<1的全球变暖潜能值(GWP)的相对新发现的有效冷却剂。R-1234yf是易燃的，尽管这个特性允许其被许多应用所接受。
相反，二氧化碳(R-744或CO2)具有1的低GWP，但是其由于高压而在传统系统中的使用被限制，其可在传统的基于R-134a的系统中发挥作用。进一步地，二氧化碳作为制冷剂使用被其蒸发温度所限制，因为其可允许蒸发器变得过冷而由从大气中回收的冷凝水形成冰。进一步地，二氧化碳可提供不利的温度滑移(当制冷剂被逐步蒸发/冷凝时蒸发和冷凝之间的总温度差)。结果是在没有对制冷系统本身进行重大调整的情况下很难有效地利用R-744，除非二氧化碳(R-744或CO2)的量被限制以免损伤标准的机动车空调系统。
本申请发现：增加了低水平的混合有R-1234yf的二氧化碳提供了一种低GWP、低易燃性、和有效的制冷剂组合物。如本领域已知的，碳氟化合物燃烧化学在很大程度上是不可预测的并且将不易燃化合物和易燃的碳氟化合物混合将减少整体易燃性或减少空气中的易燃组分的范围是非显而易见的(易燃性可根据美国采暖、制冷与空调工程师学会(American Society of Heating,Refrigerating and Air-Conditioning Engineers，ASHRAE)标准确定)。进一步地，本申请认定：在此描述的组合物中包含相对低水平的R-744为R-1234yf提供了改进的阻燃性能而不损失高于添加的少数制冷剂的百分比的冷却效率。低水平的R-744进一步提供了有效的冷却而没有明显的压力增加。
以特定比例组合的两种制冷剂提供了具有较低易燃性的有效冷却剂。组合物进一步提供了与单独的R-1234yf相比的改进的能量效率和较低的压降特性。
制冷剂组合物可包含99.9％至95％之间的R-1234yf和0.1％至5％之间的R-744(在此提及的包括在权利要求中的组合物中的所有％量是基于组合物的总重量按重量计的，除非另有说明)。在一些实施例中，制冷剂组合物仅包含R-1234yf和R-744。R-1234yf可构成制冷剂组合物的百分之99.9、99.8、99.7、99.6、99.5、99.4、99.3、99.2、99.1、99.0、98.9、98.8、98.7、98.6、98.5、98.4、98.3、98.2、98.1、98.0、97.9、97.8、97.7、97.6、97.5、97.4、97.3、97.2、97.1、97.0、96.9、96.8、96.7、96.7、96.6、96.5、96.4、96.3、96.2、96.1、96.0、95.9、95.8、95.7、95.6、95.5、95.4、95.3、95.2、95.1、95.0。R-744可构成制冷剂组合物的剩余百分比。R-744可构成制冷剂组合物的百分之0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3.0、3.1、3.2、3.3、3.4、3.5、3.6、3.7、3.8、3.9、4.0、4.1、4.2、4.3、4.4、4.5、4.6、4.7、4.8、4.9或5.0。制冷剂组合物本质上由R-1234yf和R-744组成。
还提供用在冷却系统中的组合物，该组合物包括制冷剂组合物和润滑剂。润滑剂可从聚亚烷基二醇(PAG)、聚乙烯基醚(PVE)或多元醇酯油(POE)或这些润滑油的任何混合中选择。润滑剂可影响使用的制冷剂的性能，特别是关于制冷剂与使用的润滑剂的可混合性和溶解度。选择的润滑剂可包含支链或直链的烷基。润滑剂可进一步包含丁基羟基甲苯(BHT)。润滑剂可进一步包含稳定剂，例如，二烯基化合物(diene-based compound(s))、磷酸盐、酚类化合物和环氧化合物、及它们的混合物。
组合物可进一步包含PVE和制冷剂组合物。PVE作为润滑剂存在具有意想不到的优点，即，其允许增加存在的R-744，高达大约50％，但当与R-1234yf混合时不超过99.9％。
根据额外的方面，制冷工作流体可包含大约5至55重量份的润滑剂和大约95至45重量份的制冷剂组合物。润滑剂可以10至35重量份存在。制冷剂可以90至65重量份存在。润滑剂和制冷剂应被组合以致它们在使用的系统的工作温度下仍然易混合。在整个使用的温度范围内，混浊态、絮状物或沉淀的形成、或分离成两种不同的液体层表示它们是不能混合的。
根据另一方面，阻燃剂可被添加至制冷工作流体。这样的添加剂在本领域是已知的并且包括，例如：磷酸三(2-氯乙基)酯(tri-(2-chloroethyl)-phosphate)、(氯丙)磷酸盐、磷酸三(2、3-二溴丙基)酯(tri-(2,3-dibromopropyl)-phosphate)、磷酸三(1,3-二氯丙基)酯(tri-(1,3-dichloropropyl)-phosphate)、磷酸氢二铵、各种卤代芳香族化合物、氧化锑、三水合铝、聚氯乙烯、氟化碘碳(fluorinated iodocarbon)、氟化溴碳、三氟碘甲烷、全氟烃基胺、溴氟烷基胺及它们的混合物。
更进一步地，提供了一种传热装置，其包含新型制冷剂组合物或工作流体。这样的传热装置包括，例如：机动车辆空调系统、住宅和商业的空调系统、住宅和商业的冷藏库系统、住宅和商业的冷冻库系统、冷水机空调系统、冷水机制冷系统、和热泵系统。优选地，传热装置是制冷装置或空调系统。传热装置可包含离心机类型的压缩机。
制冷剂组合物和/或制冷剂工作流体可进一步被提供为与已知起泡剂一起的发泡剂或可发泡组合物(即，能够形成泡沫)，已知起泡剂例如，聚氨酯、聚苯乙烯、环氧树脂或其它的热塑性聚合物和树脂。本发明的组合物可被提供为可喷射的组合物并与推进剂组合。
此外，新的和改进的方法被提供用于冷却对象或空间，该方法包含蒸发在要冷却的空间里或在要冷却的对象的附近的制冷剂组合物并且之后在远离该对象或空间的空间中冷凝制冷剂组合物。
在此公开的新的和新颖的组合物可用在使用不同制冷剂的传热系统中。这样的改造方法包含移除现有的传热流体并引入在此描述的组合物。
前述已经为举例说明和说明的目的而被呈现。其不旨在穷尽或限制实施例于公开的精确形式。根据上述教导明显的改进和变化是可能的。当根据权利要求的公平、合法和公平享有的宽度被解释时，所有这样的改进和变化在所附权利要求的范围内。

Claims (20)

1.一种制冷剂组合物，包含至少95％的R-1234yf和5％或更少的R-744。
2.根据权利要求1所述的制冷剂组合物，其中所述制冷剂组合物本质上由至少95％的R-1234yf和5％或更少的R-744组成。
3.根据权利要求1所述的制冷剂组合物，其中R-1234yf至少占所述制冷剂组合物的96％。
4.根据权利要求3所述的制冷剂组合物，其中R-744占少于所述制冷剂组合物的4％。
5.根据权利要求1所述的制冷剂组合物，其中R-1234yf至少占所述制冷剂组合物的97％。
6.根据权利要求5所述的制冷剂组合物，其中R-744占少于所述制冷剂组合物的3％。
7.根据权利要求1所述的制冷剂组合物，其中R-1234yf至少占所述制冷剂组合物的98％。
8.根据权利要求7所述的制冷剂组合物，其中R-744占少于所述制冷剂组合物的2％。
9.根据权利要求1所述的制冷剂组合物，其中R-1234yf至少占所述制冷剂组合物的99％。
10.根据权利要求1所述的制冷剂组合物，其中R-744占少于所述制冷剂组合物的1％。
11.根据权利要求1所述的制冷剂组合物，其中R-1234yf至少占所述制冷剂组合物的99.5％。
12.根据权利要求11所述的制冷剂组合物，其中R-744占少于所述制冷剂组合物的0.5％。
13.一种用于空调单元的组合物，包含权利要求1所述的制冷剂组合物和润滑剂。
14.根据权利要求13所述的组合物，其中所述润滑剂是从由聚亚烷基二醇、聚乙烯基醚和多元醇酯油组成的组中选择。
15.一种包含权利要求13所述的组合物的传热装置。
16.一种用于冷却空间的方法，包含操作在所述空间内的传热装置，其中所述传热装置使用权利要求8所述的组合物以从所述空间传递热。
17.一种用于空调单元的组合物，包含PVE和包含R-1234yf和大约50％或更少的R-744的制冷剂组合物。
18.根据权利要求17所述的组合物，其中所述制冷剂组合物本质上由R-744和R-1234yf组成。
19.根据权利要求18所述的组合物，其中所述制冷剂组合物是大约5％或更少的R-744。
20.一种包含权利要求17所述的制冷剂组合物的传热装置。
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