CN102471670A - 传热方法 - Google Patents
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Abstract
本发明涉及使用包含氢(氯)氟烯烃的组合物的传热方法。更具体地,本发明涉及传热方法,其相继地包括制冷剂蒸发的步骤、压缩步骤、所述制冷剂在大于或等于70℃的温度下冷凝的步骤、以及所述制冷剂膨胀的步骤,特征在于所述制冷剂包含由式(I)R1CH=CHR2表示的具有至少4个碳原子的至少一种氢氟烯烃,其中R1和R2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
Description
本发明涉及使用包含氢氟烯烃的组合物的传热方法。更具体地,本发明涉及包含氢氟烯烃的组合物在热泵中的用途。
在蒙特利尔商议了由损耗大气臭氧层(具有臭氧损耗潜势,ODP)的物质导致的问题,在蒙特利尔签署了要求减少氯氟烃(CFC)的制造和使用的议定书。已经对该议定书进行了修正,要求放弃CFC并且扩展对其它产品的控制。
制冷和空调工业已经在这些制冷剂的替代物方面进行了大量投资。
在汽车工业中,许多国家中出售的车辆用空调系统已经由氯氟烃制冷剂(CFC-12)变为对臭氧层危害较小的氢氟烃制冷剂(1,1,1,2-四氟乙烷:HFC-134a)。但是,对于由京都议定书所设定的目标,HFC-134a(GWP=1300)被认为具有高的升温效应。流体对温室效应的贡献由标准即全球增温潜势(GWP)量化,所述GWP概括了升温效应,以二氧化碳作为参考值1。
由于二氧化碳是无毒、不可燃的且具有非常低的GWP,因此已经提出将二氧化碳作为HFC-134a的替代物用作空调系统的制冷剂。但是,使用二氧化碳带来若干缺点,所述缺点特别地与在现有设备和技术中使用二氧化碳作为制冷剂时的非常高的压力有关。
文献JP 4110388描述了式C3HmFn的氢氟丙烯(特别是四氟丙烯和三氟丙烯)作为传热流体的用途,其中m、n代表1~5的整数且m+n=6,。
文献WO2004/037913公开了包含至少一种具有3个或4个碳原子的氟烯烃的组合物作为传热流体的用途,所述氟烯烃特别是五氟丙烯和四氟丙烯,优选具有至多150的GWP。
在文献WO2007/002625中,具有3-6个碳原子的氟卤代烯烃(特别是四氟丙烯、五氟丙烯和氯三氟丙烯)被描述为可用作传热流体。
文献WO2007/053697描述了包含具有至少5个碳原子的氟烯烃的传热流体。
在热泵领域中,已经提出了在高冷凝温度条件下使用的二氯四氟乙烷(HCFC-114)的替代物。因此,文献US 6814884描述了包含如下的组合物:1,1,1,3,3-五氟丁烷(HFC-365mfc);以及至少一种选自1,1,1,2-四氟乙烷、五氟乙烷(HFC-125)、1,1,1,3,3-五氟丙烷(HFC-245fa)和1,1,1,2,3,3,3-七氟丙烷(HFC-227ea)的化合物。但是,这些化合物具有高的GWP且相对于HCFC-114具有非常高的压缩比和温度降。
文献US 20090049856描述了包含1,1,1,3,3-五氟丙烷(HFC-245fa)、1,1,1,2,3,3-六氟丙烷(HFC-236ea)和四氟乙烷(HFC-134a)的传热流体。但是,这些混合物在冷凝器入口(压缩机出口)处具有非常高的温度,这意味着机械部件过热以及压缩机总效率的降低。而且,这些混合物的临界温度(约110℃)低于所需的冷凝温度(120℃或者甚至150℃),使得它们不能用于高温热泵。
本申请人现已发现:包含氢氟烯烃的组合物非常特别地适合作为热泵(尤其是在高冷凝温度下操作的热泵)中的传热流体。而且,这些组合物具有可忽略的ODP和低于现有传热流体的GWP。此外,这些混合物具有超过150℃的临界温度,因此容许它们用于高温热泵。
热泵是使得能够将热量从最冷的介质传递到最热的介质的热力学装置。用于加热的热泵被称为压缩型,且操作基于具有称为制冷剂的流体的压缩的循环的原理。这些热泵以具有单级或若干级的压缩系统起作用。在给定的级,当制冷剂被压缩并从气态转变为液态时,发生产生热量的放热反应(冷凝)。相反,如果流体膨胀,导致其从液态转变为气态,则发生产生冷觉的吸热反应(蒸发)。因此,一切基于封闭回路中所用流体的状态的变化。
压缩系统的各级包括:(i)蒸发步骤,在该蒸发步骤期间,当与从环境得到的卡路里接触时,由于制冷剂的低沸点,制冷剂从两相态(液/气)转变为气态;(ii)压缩步骤,在该压缩步骤期间,将来自前一步骤的气体升至高压;(iii)冷凝步骤,在该冷凝步骤期间,气体将其热量传递至加热回路(热环境);仍压缩的制冷剂再次变为液体;以及(iv)膨胀步骤,在该膨胀步骤期间,流体的压力降低。该流体准备好再次从冷环境吸收卡路里。
本发明涉及采用压缩系统的传热方法,所述压缩系统具有至少一个相继包括如下步骤的级:制冷剂的蒸发步骤、压缩步骤、所述流体在大于或等于70℃的温度下的冷凝步骤、以及所述流体的膨胀步骤,特征在于所述制冷剂包含至少一种由式(I)R1CH=CHR2表示的具有至少4个碳原子的氢氟烯烃,其中R1和R2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
优选地,所述氢氟烯烃的至少一个烷基被氟原子完全取代。
优选地,制冷剂的冷凝温度为70-150℃、且有利地为95-140℃。
作为特别有利的式(I)的氢氟烯烃,可特别提及1,1,1,4,4,4-六氟丁-2-烯、1,1,1,4,4,5,5,5-八氟-戊-2-烯、1,1,1,4-四氟丁-2-烯、1,1,1,4,4-五氟丁-2-烯、1,1,4-三氟丁-2-烯、1,1,1-三氟丁-2-烯、4-氯-1,1,1-三氟丁-2-烯、4-氯-4,4-二氟丁-2-烯。
优选的式(I)的氢氟烯烃可为顺式或反式、或者两者的混合。
除了式(I)的氢氟烯烃外,制冷剂可包含至少一种选自氢氟烃、烃、(氢)氟醚、氢氯氟丙烯、氢氟丙烯、醚、甲酸甲酯、二氧化碳和反式-1,2-二氯乙烯的化合物。
作为氢氟烃,可特别提及1,1,1,3,3-五氟丁烷、1,1,1,2-四氟乙烷、五氟乙烷、1,1,1,3,3-五氟丙烷、1,1,1,2,3-五氟丙烷、1,1,1,2,2-五氟丙烷、1,1,1,3,3,3-六氟丙烷、1,1,2,2,3-五氟丙烷、1,1,1,3,3-五氟丁烷、1,1,1,2,2,3,4,5,5,5-十氟戊烷和1,1,1,2,3,3,3-七氟丙烷。
优选具有至少三个碳原子的烃。尤其优选具有5个碳原子的烃如戊烷、异戊烷、环戊烷。
优选的氢氯氟丙烯为2-氯-3,3,3-三氟丙-1-烯、1-氯-3,3,3-三氟丙-1-烯,尤其是反式-1-氯-3,3,3-三氟丙-1-烯。
优选的氢氟醚为具有3-6个碳原子的那些。
作为氢氟醚,可特别提及七氟甲氧基丙烷、九氟甲氧基丁烷和九氟乙氧基丁烷。氢氟醚可以若干种同分异构形式利用,例如1,1,1,2,2,3,3,4,4-九氟-乙氧基丁烷、1,1,1,2,3,3-六氟-2-(三氟甲基)-3-乙氧基丁烷、1,1,1,2,2,3,3,4,4-九氟-甲氧基丁烷、1,1,1,2,3,3-六氟-2-(三氟甲基)-3-甲氧基丁烷和1,1,1,2,2,3,3-七氟甲氧基丙烷。
优选的氢氟丙烯为三氟丙烯如1,1,1-三氟丙烯、四氟丙烯如2,3,3,3-四氟丙烯(HFO-1234yf)和1,3,3,3-四氟丙烯(顺式和/或反式)。
醚可选自二甲醚、二乙醚、二甲氧基甲烷或二丙氧基甲烷。
优选地,制冷剂包含至少一种式(I)的氢氟烯烃和至少一种氢氟烃。所述氢氟烃有利地选自1,1,1,3,3-五氟丁烷和1,1,1,3,3-五氟丙烷。
1,1,1,4,4,4-六氟丁-2-烯或1,1,1,4,4,5,5,5-八氟戊-2-烯与甲酸甲酯、戊烷、异戊烷、环戊烷或反式-1,2-二氯乙烯的共沸组合物也可为合适的。
优选地,制冷剂包含至少10重量%的式(I)的氢氟烯烃。
根据本发明的一个实施方案,制冷剂包含:40-100重量%的1,1,1,4,4,4-六氟丁-2-烯;以及0-60重量%的至少一种选自戊烷、异戊烷、环戊烷和反式-1,2-二氯乙烯的化合物。
作为特别优选的制冷剂,可提及包含60-100重量%的1,1,1,4,4,4-六氟丁-2-烯和0-40重量%的环戊烷、戊烷、异戊烷或反式-1,2-二氯乙烯的那些。
本发明中所用的制冷剂可包含氢氟烯烃的稳定剂。相对于流体的总组成,该稳定剂占至多5重量%。
作为稳定剂,可特别提及:硝基甲烷;抗坏血酸;对苯二甲酸;唑,例如甲苯并三唑(tolutriazole)或苯并三唑;酚化合物,例如生育酚、对苯二酚、叔丁基对苯二酚、2,6-二-叔丁基-4-甲基苯酚;环氧化物(烷基环氧化物(任选地被氟化或全氟化)、或者烯基或芳族环氧化物),例如正丁基缩水甘油醚、己二醇二缩水甘油醚、烯丙基缩水甘油醚、丁基苯基缩水甘油醚;亚磷酸酯;磷酸酯;膦酸酯;硫醇;和内酯。
根据本发明的方法中所用的制冷剂可包含润滑剂,例如矿物油、烷基苯、聚α烯烃、聚亚烷基二醇、多元醇酯和聚乙烯基醚。与制冷剂一起使用的润滑剂可包含用于改善流体的导热性以及流体与润滑剂的相容性的纳米颗粒。作为纳米颗粒,可特别提及Al2O3或TiO2的颗粒。
与制冷剂一起使用的润滑剂可包含沸石型减湿剂。沸石吸收水,并从而限制腐蚀和性能劣化。
实验部分
在下文中:
Evap:蒸发器,
Cond:冷凝器,
Temp:温度,
Comp:压缩机,
P:压力,
比:压缩比
COP:性能系数,对于热泵,其定义为由体系提供的有用高温功率与供给至体系或由体系消耗的功率之比
CAP:体积容量,其为每单位体积的加热热容(kJ/m3)
%CAP或COP是流体的CAP或COP值相对于用HCFC-114获得的CAP或COP值之比。
实施例1
下面给出在蒸发器处的温度保持为30℃、压缩机入口处的温度保持为35℃且冷凝器处的温度为90℃的热泵操作条件下的制冷剂性能。
将各产品的COP计算为HCFC114或R114的COP的百分数。
压缩机的等熵效率:59.3%
C 异戊烷
E 反式-1,2-二氯乙烯
H 戊烷
J 1,1,1,4,4,4-六氟丁-2-烯
结果表明:相对于参比产品(R114),COP提高。
二元混合物(H,J)和(C,J)具有与R114的值相当的COP、冷凝器入口温度和压缩比,且这些产品为温度降的值低于2.2℃的准共沸物。
产品J以及混合物(E,J)具有比参比产品(R114)的COP高5%的COP。
实施例2
下面给出在蒸发器处的温度保持为80℃、压缩机入口处的温度保持为85℃且冷凝器处的温度为140℃的热泵操作条件下的制冷剂性能。
将各产品的COP和CAP分别计算为R114的COP和CAP的百分数。
压缩机的等熵效率:59.3%
C 异戊烷
E 反式-1,2-二氯乙烯
H 戊烷
J 1,1,1,4,4,4-六氟丁-2-烯
结果表明:新产品的COP远大于参比(R114)的COP。
Claims (10)
1.采用压缩系统的传热方法,所述压缩系统具有至少一个相继包括如下步骤的级:制冷剂的蒸发步骤、压缩步骤、所述流体在大于或等于70℃的温度下的冷凝步骤、以及所述流体的膨胀步骤,特征在于所述制冷剂包含至少一种由式R1CH=CHR2表示的具有至少4个碳原子的氢氟烯烃,其中R1和R2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
2.权利要求1的方法,特征在于所述温度为70-150℃、优选95-140℃。
3.权利要求1或2的方法,特征在于所述制冷剂进一步包含至少一种选自氢氟烃、烃、(氢)氟醚、氢氯氟丙烯、氢氟丙烯、醚、甲酸甲酯、二氧化碳和反式-1,2-二氯乙烯的化合物。
4.权利要求1-3中任一项的方法,特征在于所述制冷剂包含至少一种选自1,1,1,3,3-五氟丁烷和1,1,1,3,3-五氟丙烷的氢氟烃。
5.权利要求1-4中任一项的方法,特征在于所述制冷剂包含至少一种选自戊烷、异戊烷和环戊烷的烃。
6.权利要求1-5中任一项的方法,特征在于所述制冷剂包含40-100重量%的1,1,1,4,4,4-六氟丁-2-烯、以及0-60重量%的至少一种选自戊烷、异戊烷、环戊烷和反式-1,2-二氯乙烯的化合物。
7.权利要求1-6中任一项的方法,特征在于所述制冷剂包含60-100重量%的1,1,1,4,4,4-六氟丁-2-烯、以及0-40重量%的环戊烷、戊烷、异戊烷或反式-1,2-二氯乙烯。
8.权利要求1-7中任一项的方法,特征在于所述制冷剂包含稳定剂。
9.权利要求1-8中任一项的方法,特征在于所述制冷剂包含润滑剂。
10.权利要求9的方法,特征在于所述润滑剂为聚亚烷基二醇、多元醇酯或聚乙烯基醚。
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PCT/FR2010/051279 WO2011015737A1 (fr) | 2009-07-28 | 2010-06-23 | Procede de transfert de chaleur |
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JP7444719B2 (ja) | 2020-07-10 | 2024-03-06 | ダイキン工業株式会社 | 2-クロロ-1,1-ジフルオロエタン(hcfc-142)、1,1,2-トリフルオロエタン(hfc-143)、及び(e)-1,2-ジフルオロエチレン(hfo-1132(e))及び/又は(z)-1,2-ジフルオロエチレン(hfo-1132(z))の製造方法 |
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US20190040292A1 (en) | 2019-02-07 |
JP2019032155A (ja) | 2019-02-28 |
JP6021642B2 (ja) | 2016-11-09 |
JP2016197007A (ja) | 2016-11-24 |
WO2011015737A1 (fr) | 2011-02-10 |
JP2013500373A (ja) | 2013-01-07 |
US20220119694A1 (en) | 2022-04-21 |
EP3176239A1 (fr) | 2017-06-07 |
FR2948678B1 (fr) | 2011-10-14 |
CN102471670B (zh) | 2015-07-01 |
EP2459667A1 (fr) | 2012-06-06 |
US20120117990A1 (en) | 2012-05-17 |
EP2459667B1 (fr) | 2017-02-22 |
ES2619933T3 (es) | 2017-06-27 |
PL2459667T3 (pl) | 2017-06-30 |
FR2948678A1 (fr) | 2011-02-04 |
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