CN105074355B - 吸收式热泵以及用于吸收式热泵的包括甲磺酸的吸附介质 - Google Patents
吸收式热泵以及用于吸收式热泵的包括甲磺酸的吸附介质 Download PDFInfo
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 title claims abstract description 68
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- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
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- TXQRXFCXNQJYMA-UHFFFAOYSA-N methanesulfonic acid 2-methyl-1H-imidazole Chemical compound CS(=O)(=O)O.CC=1NC=CN1 TXQRXFCXNQJYMA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B15/00—Sorption machines, plants or systems, operating continuously, e.g. absorption type
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/04—Heat pumps of the sorption type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明涉及将甲磺酸作为吸收式热泵的吸附介质的应用；吸收式热泵的吸附介质，其包括甲磺酸和离子液体；以及包括吸收器、解吸器、冷凝器、蒸发器和工作介质的吸收式热泵，该工作介质包括挥发性制冷剂和吸附介质，其中吸附介质包括甲磺酸。
Description
本发明涉及吸收式热泵，以及用于吸收式热泵的吸附介质，该吸附介质包括甲磺酸。
典型的热泵基于通过蒸发器和冷凝器的制冷剂循环。蒸发器中，制冷剂被蒸发，其中通过被制冷剂获取的蒸发热量而从第一介质得到热量。然后被蒸发的制冷剂借助于压缩机被压缩至更高的压力并在冷凝器中在高于蒸发过程的温度下冷凝，其中蒸发热量再次被释放，且热量在更高的温度水平被传递至第二介质。液化的制冷剂随后被再次降压至蒸发器的压力。
典型的热泵具有如下缺点，其耗费大量的机械能以压缩蒸汽态制冷剂。另一方面，吸收式热泵对机械能需求较少。吸收式热泵除了具有典型热泵的制冷剂、蒸发器和冷凝器之外，还具有吸附介质、吸收器和解吸器。蒸发的制冷剂在蒸发压力下在吸收器中被吸附介质吸收，且随后在较高的冷凝压力下通过供应的热量在解吸器中再从吸附介质中解吸。与典型的热泵中的制冷剂蒸汽的压缩过程相比，制冷剂和吸附介质组成的液体工作介质的压缩需要较少的机械能，且机械能的消耗被制冷剂解吸过程中所用的热能所代替。吸收式热泵的能效计算为用于制冷和加热的热流与吸收式热泵运行中供应至解吸器的热流的比值，被称为“性能系数”，简称为COP。
大部分工业上应用的吸收式热泵使用的工作介质包括用作制冷剂的水和用作吸附介质的溴化锂。然而该工作介质具有缺点，水在工作介质中的浓度必须不低于35-40重量％，否则会导致溴化锂的结晶并且由此导致故障直至工作介质固化。
WO2005/113702和WO2006/134015中，提供使用包含具有有机阳离子的离子液体作为吸附介质的工作介质，以避免由于吸附介质结晶导致的故障。这些工作介质具有缺点，其在低含量的制冷剂时具有不需要的高粘性。
包含作为吸附介质的硫酸的工作介质同样具有缺点，其在低含量的制冷剂时具有不需要的高粘性。另外，它们也是非常具有腐蚀性的。
因此存在吸收式热泵的吸附介质的持续需求，通过其吸收式热泵既能达到好的能效，也不会因吸附介质结晶而产生问题，以及工作介质同时具有低粘性和可控的腐蚀性。
现在已经发现通过使用甲磺酸，尤其是将甲磺酸与离子液体结合使用作为吸附介质能达到这种组合性能。
本发明相应地提供一种吸收式热泵，其包括吸收器、解吸器、冷凝器、蒸发器和工作介质，其中工作介质包括挥发性的制冷剂和吸附介质，且吸附介质包括甲磺酸。
此外本发明还提供一种用于吸收式热泵的吸附介质，该吸附介质包括甲磺酸和离子液体。
本发明进一步地提供甲磺酸用作吸收式热泵中的吸附介质的用途。
为了本发明的上述目的，术语吸收式热泵包括热量从低温水平获取、并在高温水平再次释放且由供给解吸器的热量来驱动的所有装置。因此本发明的吸收式热泵在狭义中包括吸收式制冷机器和吸收式热泵，其中与解吸器和冷凝器相比，吸收器和蒸发器在较低工作压力下运行，且在吸收式热转换器中，与解析器和冷凝器相比，吸收器和蒸发器在较高工作压力下运行。在吸收式制冷机器中，从蒸发器的蒸发中获取的热量用于冷却介质。在吸收式热泵中，狭义地说，冷凝器和/或吸收器中释放的热量用于加热介质。在吸收式热转换器中，吸收器中释放的吸收热量用于加热介质，该吸收热量在高于供应至解吸器的热量的温度水平获得。
本发明的吸收式热泵包括吸收器、解吸器、冷凝器、蒸发器和工作介质，工作介质包括挥发性的制冷剂和吸附介质。
本发明的吸收式热泵的运行中，蒸汽态制冷剂在吸收器中被贫制冷剂的工作介质吸收以形成富含制冷剂的工作介质，并释放吸收热量。解吸器中被供给热量，由此制冷剂从如此获得的富含制冷剂的工作介质中以蒸汽态解吸，以形成贫制冷剂的工作介质，且该工作介质再次循环至吸收器。解吸器中获得的蒸汽态制冷剂在冷凝器中被冷凝，并释放冷凝热量，获得的液体制冷剂在蒸发器中蒸发且吸收蒸发热量，在此获得的蒸汽态制冷剂再次循环至吸收器。
在一个优选实施方案中，吸收式热泵为吸收式制冷机器，且在蒸发器中从待冷却的介质中获得热量。
本发明的吸收式热泵的工作介质包括挥发性制冷剂和包括甲磺酸的吸附介质。适合的挥发性制冷剂为沸点在-90～120℃范围内且与甲磺酸不可逆反应的物质。本发明的吸收式热泵的工作介质优选包含水作为制冷剂。
在一个优选实施方案中，吸附介质中的水和甲磺酸的组合含量为大于90重量％。
在另一个优选实施方案中，吸附介质包括甲磺酸和离子液体。甲磺酸和离子液体的重量比优选在9∶1到1∶100的范围内。在甲磺酸和离子液体为高重量比时，优选在范围9∶1到1∶4的范围，更优选地在9∶1到1∶1的范围，能达到吸收器中所需温度下制冷剂的低蒸汽压力以及吸收器和解吸器所需的温度之间的高的蒸汽压力差。甚至在甲磺酸与离子液体的低重量比时，优选在1∶1到1∶100的范围，更优选地在1∶4到1∶100的范围，甚至更优选地在1∶10到1∶100的范围内，与仅使用离子液体作为吸收介质的工作介质相比，本发明的工作介质可以达到明显更低的粘度和改进的热稳定性。此外，在甲磺酸与离子液体的重量比在9∶1到1∶10的范围，优选地在1∶1到1∶10的范围，更优选地在1∶1到1∶4的范围内时，包含水作为制冷剂的工作介质在解吸器所需的温度下令人惊异地达到了非理想的具有升高的蒸汽压力的蒸汽压力性能。
术语离子液体指的是由阴离子和阳离子组成的盐或盐混合物，其中盐或盐混合物具有低于100℃的熔点。术语离子液体指的是不含非离子物质或添加物的盐或盐混合物。离子液体优选由一种或多种具有有机阳离子和有机或无机阴离子的盐组成。离子液体优选具有低于20℃的熔点，以避免在吸收式热泵中使用工作介质时吸附介质循环中的离子液体固化。
适合本发明的吸附介质的离子液体具有强酸的阴离子，优选为具有pKa小于0的酸。适合的阴离子为硝酸根、高氯酸根、硫酸氢根、式RaOSO3 -和RaSO3 -的阴离子，其中Ra为具有1-30个碳原子的直链或支链的脂族烃基、具有5-40个碳原子的脂环族烃基、具有6-40个碳原子的芳族烃基、具有7-40个碳原子的烷基芳基或具有1-30个碳原子的直链或支链全氟烷基，以及式RaOSO3 -和RaSO3 -的其中Ra为聚醚基的阴离子。阴离子优选为硝酸根、硫酸氢根、甲磺酸根、甲基硫酸根或乙基硫酸根，更优选地为甲磺酸根。
离子液体的一种或多种有机阳离子可以带一个、两个或多个正电荷且优选为带一个正电荷。离子液体的一种或多种有机阳离子优选具有不高于260g/mol的分子量，特别地优选为不超过220g/mol，尤其是不超过195g/mol，最优选地是不超过170g/mol。对阳离子的分子量的限制改进了吸收式热泵运行中的工作介质脱气范围。
适合的有机阳离子特别是通式(I)到(V)的阳离子：
R1R2R3R4N+ (I)
R1R2R3R4P+ (II)
R1R2R3S+ (III)
R1R2N+＝C(NR3R4)(NR5R6) (IV)
R1R2N+＝C(NR3R4)(XR5) (V)
其中，R1、R2、R3、R4、R5、R6相同或不同，且为氢、直链或支链的脂族烃基、脂环族烃基、芳族烃基、烷基芳基或式-(R7-O)n-R8的聚醚基，其中式(V)R5中的阳离子不是氢，
R7为具有2或3个碳原子的直链或支链亚烷基，
n为1到3，
R8为直链或支链的脂族烃基，
X为氧原子或硫原子，以及
其中至少一个，优选地每一个R1、R2、R3、R4、R5和R6都不为氢。
式(I)到(V)的阳离子中的基团R1和R3共同构成4-至10-元环，优选地5-至6-元环也同样适用。
同样适用的阳离子为在环中具有至少一个季氮原子的杂芳族阳离子，且该季氮原子带有如上定义的基团R1，在氮原子上被取代的衍生物优选为吡咯、吡唑、咪唑、噁唑、异噁唑、噻唑、异噻唑、吡啶、嘧啶、吡嗪、吲哚、喹啉、异喹啉、噌啉、喹喔啉或酞嗪。
有机阳离子优选具有一个季氮原子。有机阳离子优选为1-烷基咪唑鎓离子、1，3-二烷基咪唑鎓离子、1，3-二烷基咪唑啉鎓离子、N-烷基吡啶鎓离子、N，N-二烷基吡咯烷鎓离子或者具有R1R2R3R4N+结构的铵离子，其中R1、R2和R3各自独立地为氢或烷基且R4为烷基。
在一个优选实施方案中，有机阳离子为1，3-二烷基咪唑鎓离子，其中烷基优选各自独立地选自甲基、乙基、正丙基和正丁基。
离子液体优选为1，3-二甲基咪唑鎓甲磺酸盐、1-乙基-3-甲基咪唑鎓甲磺酸盐、1，3-二乙基咪唑鎓甲磺酸盐、1，3-二甲基咪唑鎓甲基硫酸盐、1-乙基-3-甲基咪唑鎓甲基硫酸盐、1-乙基-3-甲基咪唑鎓乙基硫酸盐和1，3-二乙基咪唑鎓乙基硫酸盐。更优选地为1，3-二甲基咪唑鎓甲磺酸盐、1-乙基-3-甲基咪唑鎓甲磺酸盐和1，3-二乙基咪唑鎓甲磺酸盐，最优选地为1，3-二甲基咪唑鎓甲磺酸盐。
离子液体可通过现有技术已知的方法制备，如P.Wasserscheid，T.Welton，IonicLiquids in Synthesis，第二版，Wiley-VCH(2007)，ISBN 3-527-31239-0中或在Angew.Chemie 112(2000)第3926-3945页所公开的。
离子液体优选在20℃为液体，且在此温度下具有根据DIN 53 019的1-15000mPa·s的粘度，特别优选为2-10000mPa·s，更优选地5-5000mPa·s以及最优选为10-3000mPa·s。在50℃下，离子液体优选具有小于3000mPa·s的粘度，特别的优选小于2000mPa·s，以及更优选地小于1000mPa·s。
优选使用的离子液体可以与水不限制地混合、是水解稳定的并且最高到100℃的温度是热稳定的。
水解稳定的离子液体在与50重量％的水混合时在80℃下储存8000小时显示出少于5％的由于水解的分解。
最高到100℃的温度是热稳定的离子液体在热重量分析中显示出小于20％的重量减少，该热重量分析在氮气环境下以10℃/分钟的加热速度从25℃加热至100℃而进行。尤其优选的离子液体在该分析中显示出小于10％和特别地小于5％的重量减少。
在吸收式热泵中使用甲磺酸作为吸附介质的用途避免了当吸附介质为溴化锂时发生的吸附介质结晶的问题。与硫酸作为吸附介质相比，甲磺酸具有吸附介质较低腐蚀性的优点。与纯的离子液体相比，甲磺酸具有低粘度以及对于水的高吸收能力的优点。
使用本发明的吸附介质(其包括与离子液体结合使用的甲磺酸)可以达到特别好的吸附介质的低腐蚀、低粘度、高热稳定性以及对于水的高吸收能力的特点集合。
下面的实施例说明了本发明，但是并非限制本发明的主题。
实施例：
实施例1-5
对于含有15重量％的作为制冷剂的水和85重量％的由甲磺酸(MeSO3H)和1，3-二甲基咪唑鎓甲磺酸盐(MMIM MeSO3)组成的吸附介质的工作介质，在35℃和80℃下测定蒸汽压力。研究的甲磺酸和1，3-二甲基咪唑鎓甲磺酸盐的重量含量和由此获得的结果总结在表1中。
表1
由15重量％的水和85重量％的吸附介质构成的工作介质的蒸汽压力。
*不是根据本发明。
Claims (13)
1.吸收式热泵，包括吸收器、解吸器、冷凝器、蒸发器和包括挥发性制冷剂以及吸附介质的工作介质，其特征在于：吸附介质包括甲磺酸。
2.根据权利要求1的吸收式热泵，其特征在于：其为吸收式制冷机器，且在蒸发器中从待冷却的介质中获得热量。
3.根据权利要求1的吸收式热泵，其特征在于：其包括水作为制冷剂。
4.根据权利要求2的吸收式热泵，其特征在于：其包括水作为制冷剂。
5.用于吸收式热泵的吸附介质，其特征在于：其包括甲磺酸和离子液体。
6.根据权利要求5的吸附介质，其特征在于：甲磺酸和离子液体的重量比在9:1到1:4的范围内。
7.根据权利要求5的吸附介质，其特征在于：甲磺酸和离子液体的重量比在1:4到1:100的范围内。
8.根据权利要求5到7任一项的吸附介质，其特征在于：其包括1,3-二烷基咪唑鎓盐作为离子液体。
9.根据权利要求8的吸附介质，其特征在于：1,3-二烷基咪唑鎓盐选自1,3-二甲基咪唑鎓甲磺酸盐、1-乙基-3-甲基咪唑鎓甲磺酸盐和1,3-二乙基咪唑鎓甲磺酸盐。
10.根据权利要求1-4任一项的吸收式热泵，其特征在于：其包括根据权利要求5-9任一项的吸附介质。
11.甲磺酸的用途，其中使用所述甲磺酸作为在吸收式热泵中的吸附介质。
12.根据权利要求11的用途，其特征在于：所述吸收式热泵是吸收式制冷机器且在蒸发器中从待冷却的介质中获得热量。
13.根据权利要求11或12的用途，其特征在于：甲磺酸用作根据权利要求5-9任一项的吸附介质。
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| PCT/EP2013/072972 WO2014079675A1 (de) | 2012-11-21 | 2013-11-05 | Absorptionswärmepumpe und sorptionsmittel für eine absorptionswärmepumpe umfassend methansulfonsäure |
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