CN1537153A - 用于燃料电池驱动器中冷却系统的含吡咯衍生物的冷却剂 - Google Patents
用于燃料电池驱动器中冷却系统的含吡咯衍生物的冷却剂 Download PDFInfo
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- 239000002826 coolant Substances 0.000 title claims abstract description 26
- 239000000446 fuel Substances 0.000 title claims description 35
- 150000007980 azole derivatives Chemical class 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 34
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- 239000012141 concentrate Substances 0.000 claims abstract description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
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- 150000003233 pyrroles Chemical class 0.000 claims description 25
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
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- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 7
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
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- 239000004809 Teflon Substances 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- VRFQDZQUTDJJMF-UHFFFAOYSA-N toluene;2h-triazole Chemical compound C1=CNN=N1.CC1=CC=CC=C1 VRFQDZQUTDJJMF-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
本发明涉及一种用于燃料电池驱动器中冷却系统的防冻浓缩物,其用于生产电导率至多为50μs/cm的即用型含水冷却剂组合物,该浓缩物基于烷撑二醇或其衍生物并含有一种或多种具有2或3个选自氮和硫的杂原子的五元杂环化合物(吡咯衍生物),所述化合物不含或含有至多一个硫原子,并且可以携带稠合芳族的或饱和的六元环。
Description
本发明涉及用于燃料电池中冷却系统、特别是用于机动车的、基于烷撑二醇或其衍生物的冷却剂,其包括特定的吡咯衍生物作为缓蚀剂。
用于机动车用发动机的燃料电池甚至在低至约-40℃的室外温度下也必须能够运行。因此防冻冷却剂回路是重要的。
如果没有完全的电绝缘冷却管道,在内燃机中使用的常规散热器保护组合物是不可能在燃料电池中使用的,因为由于其中存在作为缓蚀剂的盐和离子型化合物,这些组合物具有较高的电导率,这会负面影响燃料电池的功能。
DE-A 198 02 490(1)描述了具有冷冻保护冷却回路的燃料电池,其中使用的冷却剂是倾点低于-40℃的烷烃异构体混合物。但是,这类冷却剂的缺点在于其可燃性。
EP-A 1 009 050(2)公开了用于汽车的燃料电池系统,其中使用的冷却介质是空气。但是,正如众所周知的,此时的缺点在于与液体冷却介质相比,空气是不良的热导体。
WO 00/17951(3)描述了一种用于燃料电池的冷却系统,其中使用的冷却剂是比例为1∶1的纯单乙二醇/水混合物,且没有添加剂。因为,由于缺乏缓蚀剂,对于冷却系统中存在的金属绝对没有腐蚀保护,所以冷却剂回路中包含离子交换单元,以保持冷却剂的纯度并确保在延长时间内的低比电导率,防止短路和腐蚀。可提及的合适的离子交换剂是阴离子树脂,例如强碱性羟基型,和阳离子树脂,例如基于磺酸基的树脂,以及其它过滤装置,例如活性碳过滤器。
通过(3)的实施例描述了用于汽车的燃料电池的构造和运行模式,特别是具有电子传导电解质膜的燃料电池(“PEM燃料电池”,“聚合物电解质膜燃料电池”),其中在冷却回路(散热器)中优选的金属组分是铝。
DE-A 100 63 951(4)描述了用于燃料电池驱动器中冷却系统的冷却剂,其包含原硅酸盐作为缓蚀剂。
一段时间以来,人们已经知道在用于使用汽油或柴油运行的传统内燃机的散热保护组合物中,吡咯衍生物例如苯并咪唑、苯并三唑或甲苯并三唑可以作为缓蚀剂,例如,G.Reinhard等,“Aktiver Korresionsschutz inwβrigen Medien”,87-98页,expert-Verlag 1995(ISBN 3-8169-1265-6)。
但迄今为止,这类吡咯衍生物在用于燃料电池驱动器中冷却系统的冷却剂中的使用尚未公开。
燃料电池驱动器的冷却系统中的主要问题是保持冷却剂的低电导率,以确保安全和燃料电池的无故障运行,并防止短路和长期的腐蚀。
令人惊讶的是,现已发现,在基于烷撑二醇/水的冷却系统中,以及特别是如果其包含根据(3)的整合离子交换剂的情况下,通过加入少量吡咯衍生物,可以明显延长低电导率的持续时间。由此提供的实际优点在于,可以进一步延长燃料电池驱动器中两个冷却剂更换之间的时间间隔,而这对汽车部门特别重要。
因此,我们已经发现了用于燃料电池驱动器中冷却系统的基于烷撑二醇或其衍生物的防冻浓缩物,它提供电导率至多为50μs/cm的即用型含水冷却剂组合物,其包括一种或多种具有2或3个选自氮和硫的杂原子的五元杂环化合物(吡咯衍生物),所述化合物不含或至多含有一个硫原子,并且可以携带稠合芳族或饱和的六元环。此处优选防冻浓缩物总共含有0.05-5%重量、特别是0.075-2.5%重量、尤其是0.1-1%重量的上述吡咯衍生物。
这些五元杂环化合物(吡咯衍生物)通常包含作为杂原子的两个N原子且不含S原子,3个N原子且不含S原子,或一个N原子和一个S原子。
优选的所述吡咯衍生物是通式(I)或(II)的稠合咪唑和稠合1,2,3-三唑:
其中变量R是氢或C1-C10烷基,特别是甲基或乙基,变量X是氮原子或C-H基团。通式(I)的吡咯衍生物的典型例子是苯并咪唑(X=C-H,R=H)、苯并三唑(X=N,R=H)和甲苯三唑(甲苯基三唑)(X=N,R=CH3)。通式(II)的吡咯衍生物的典型例子是氢化的1,2,3-甲苯三唑(甲苯基三唑)(X=N,R=CH3)。
更优选的所述吡咯衍生物包括通式(III)的苯并噻唑:
其中变量R定义如上,变量R’是氢、C1-C10烷基,特别是甲基或乙基,或特别是巯基(-SH)。通式(III)的吡咯衍生物的典型例子是2-巯基苯并噻唑。
此外优选通式(IV)的非稠合吡咯衍生物。
其中变量X和Y一起是两个氮原子,或一个氮原子和一个C-H基团,例如1H-1,2,4-三唑(X=Y=N)或咪唑(X=N,Y=C-H)。
本发明的吡咯衍生物更特别优选是苯并咪唑、苯并三唑、甲苯三唑、氢化甲苯三唑或其混合物。
所述吡咯衍生物可以从市场上购买或按照常规方法制备。氢化苯并三唑和氢化甲苯三唑同样可以按照DE-A 1 948 794(5)得到,以及从市场购买。
除了所述吡咯衍生物,本发明的防冻浓缩物优选如(4)中所述,还包括原硅酸盐。这类原硅酸盐的典型例子是四烷氧基硅烷,例如四乙氧基硅烷。这里优选这样的防冻浓缩物,特别是那些总共含0.05-5%重量的所述吡咯衍生物,能提供硅含量为2-2000ppm重量、特别优选25-500ppm重量硅的即用型含水冷却剂组合物的那些。
用去离子水稀释本发明的防冻浓缩物,可以提供电导率至多为50μs/cm的即用型含水冷却剂组合物,基本组成为:
(a)10-90%重量的烷撑二醇或其衍生物。
(b)90-10%重量的水。
(c)0.005-5%重量、特别是0.0075-2.5%重量、尤其是0.01-1%重量的所述吡咯衍生物,和
(d)如果需要,原硅酸盐。
此处所有组分的总和是100%重量。
本发明因此还涉及用于燃料电池驱动器中冷却系统的即用型含水冷却剂组合物,其基本组成为:
(a)10-90%重量的烷撑二醇或其衍生物。
(b)90-10%重量的水。
(c)0.005-5%重量、特别是0.0075-2.5%重量、尤其是0.01-1%重量的所述吡咯衍生物,和
(d)如果需要,原硅酸盐。
并且其可以通过用去离子水稀释所述防冻浓缩物而得到。此处所有组分的总和是100%重量。
本发明的即用型含水冷却剂组合物具有至多50μs/cm、特别是25μs/cm、优选10μs/cm、特别优选5μs/cm的初始电导率。在燃料电池驱动器长期运行数周或数月后,特别是在燃料电池驱动器中使用具有整合离子交换剂的冷却系统时,电导率保持在这个低水平。
本发明的即用型含水冷却剂组合物的pH在运行期间的下降明显慢于没有加入所述吡咯衍生物的冷却液的情况。在本发明的新鲜冷却剂组合物的情况下,pH一般在4.5-7的范围内,并且在长期运行时通常下降至3.5。用于稀释的去离子水可以是已经例如通过离子交换而去离子的纯蒸馏水或双蒸水。
在即用型含水冷却剂组合物中,烷撑二醇或其衍生物与水的优选混合重量比是20∶80至80∶20,特别是25∶75至75∶25,优选65∶35至35∶65,尤其是60∶40至40∶60。此处可使用的烷撑二醇组分或其衍生物特别是单乙二醇,但是也可以是单丙二醇、聚乙二醇类、乙二醇醚或丙三醇,在每种情况下可以是单独的或混合物的形式。特别优选是单独的单乙二醇,或以单乙二醇为主要组分的与其它烷撑二醇或烷撑二醇衍生物的混合物,即在混合物中的单乙二醇含量大于50%重量、特别是大于80%重量、尤其是大于95%重量。
本发明的可以提供即用型含水冷却剂组合物的防冻浓缩物本身可以通过将所述吡咯衍生物溶于不含水或水含量较低(例如至多10%重量,特别是至多5%重量)的烷撑二醇或其衍生物而制备。
本发明还涉及具有2或3个选自氮和硫的杂原子且其中不含或至多含一个硫原子并可以携带稠合芳族或饱和六元环的五元杂环化合物(吡咯衍生物),用于制备燃料电池驱动器的冷却系统中、特别是用于机动车的基于烷撑二醇或其衍生物的防冻浓缩物的用途。
本发明更涉及这些防冻浓缩物用于制备燃料电池驱动器的冷却系统中、特别是用于机动车的、电导率至多为50μs/cm的即用型含水冷却剂组合物的用途。
本发明的冷却剂组合物也可用于DE-A 101 04 771(6)所述的燃料电池单元,其中将冷却介质额外地以电化学方式去离子化,以防止腐蚀。
实施例
在以下实施例中解释本发明,但并不对其构成限制。
在以下描述的测试中,测试本发明的冷却剂组合物对于燃料电池驱动器的适用性,与(3)中描述的冷却剂组合物进行比较。
实验描述
将5个铝测试金属制品(真空焊接的Al,名称:EN-AW 3005,在一侧焊接电镀10%重量的EN-AW 4045;尺寸:58×26×0.35mm,带有直径7mm的洞)称重,通过带垫圈的塑料螺钉与特富龙圆盘以非传导方式连接,并放置在位于带磨砂玻璃接口和玻璃盖的1升烧杯中的特富龙架子上。随后引入1000ml测试液。在下表1所示的实验中,将一个装有2.5g离子交换剂(来自Rohm+Haas的AMBERJETUP 6040 RESIN混床离子交换树脂)的小纤维袋悬浮在液体中,并在不存在离子交换剂的情况下进行下表2所示的实验。将烧杯以气密方式用玻璃盖密封并加热至88℃,使用电磁搅拌器充分搅拌液体。在实验开始以及在数周的间隔中,对预先采集的液体样品测量电导率(来自WTW/Weilheim的LF 530电导计)。在实验完成后,对铝样品进行目测,然后在用铬酸/磷酸水溶液酸洗之后,根据ASTM D1384-94的重量分析评价。
结果见表1和2所示。
表1:在离子交换剂存在下的实验
冷却剂组合物 | 对比实施例(根据WO00/17951):60体积%MEG40体积%水 | 实施例1:60体积%MEG40体积%水0.1%重量苯并咪唑 | 实施例2:60体积%MEG40体积%水0.1%重量苯并三唑 | 实施例3:60体积%MEG40体积%水0.1%重量甲苯三唑 | 实施例4:60体积%MEG40体积%水0.1%重量氢化甲苯三唑 | 实施例5:60体积%MEG40体积%水0.05%重量苯并三唑371ppm重量四乙氧基硅烷 |
电导率[mS/cm0]实验开始:7天后:35天后:42天后:56天后: | 2.02.3---36.2--- | 4.94.27.6------ | 3.31.54.13.97.8 | 3.11.510.2------ | 1.10.8---3.5--- | 1.91.52.53.35.5 |
pH实验开始:实验结束: | 6.92.9 | 7.56.5 | 5.03.8 | 5.53.9 | 6.64.0 | 5.53.7 |
实验后铝样品的外观:酸洗后的重量变化[mg/cm2]:12345样品平均值 | 轻微失去光泽-0.05-0.04-0.04-0.04-0.03-0.04 | 失去光泽-0.07-0.06-0.06-0.06-0.07-0.06 | 失去光泽-0.06-0.06-0.06-0.06-0.06-0.06 | 失去光泽-0.01-0.01-0.01-0.01-0.01-0.01 | 失去光泽-0.04-0.05-0.05-0.05-0.05-0.05 | 失去光泽-0.03-0.04-0.02-0.03-0.03-0.03 |
实验结束时的溶液 | 浅黄色,澄清 | 浅褐色,澄清 | 无色,澄清 | 无色,澄清 | 无色,澄清 | 无色,澄清 |
在单乙二醇(=MEG)和水的混合物中,体积比60∶40对应于重量比62.5∶37.5。
在本发明的实施例5中,计量加入原硅酸盐,使得冷却液中存在的硅含量是50ppm重量。
表1的结果表明,在本发明的实施例2和4中,即使在42天的不间断实验持续时间之后,仍保持低于4μS/cm的这一非常低的电导率,而在根据WO 00/17951(3)中未加入添加剂的冷却剂中,电导率明显不利地上升至接近40μS/cm。在本发明的实施例2和5中,即使在56天的不间断实验持续时间后,电导率在某些情况下仍然明显低于8μS/cm。
在铝样品上没有发生明显的腐蚀。
表2:无离子交换剂的实验
冷却剂组合物 | 实施例1:60体积%MEG40体积%水0.1%重量苯并三唑 | 实施例2:60体积%MEG40体积%水0.1%重量苯并三唑742ppm重量四乙氧基硅烷 | 实施例3:60体积%MEG40体积%水0.1%重量氢化甲苯三唑 |
电导率[μS/cm]实验开始:7天后:14天后:28天后:35天后:42天后:49天后:56天后:63天后:77天后: | 3.25.05.88.211.213.116.1--------- | 3.25.65.26.96.97.97.67.87.16.6 | 2.15.88.69.39.717.5 |
pH实验开始:实验结束: | 5.03.6 | 5.04.9 | 5.23.4 |
实验后铝样品的外观:酸洗后的重量变化[mg/cm2]:12345样品平均值 | 几乎不变-0.010.000.000.000.000.00 | 几乎不变0.000.000.000.000.000.00 | 失去光泽-0.02-0.02-0.04-0.04-0.04-0.03 |
实验结束时的溶液 | 无色,澄清 | 无色,澄清 | 无色,澄清 |
在单乙二醇(=MEG)和水的混合物中,体积比60∶40对应于重量比62.5∶37.5。
在本发明的实施例2中,原硅酸盐计量加入,使得冷却液中存在的硅含量是100重量。
表2的结果表明,在本发明的实施例2中,即使在77天的不间断实验持续时间之后,仍保持低于10μS/cm的这一非常低的电导率;在本发明的实施例3中,在77天后的电导率仍然明显低于20μS/cm。
在这些实验中,铝样品上未出现腐蚀或无明显的腐蚀。
Claims (9)
1.一种用于燃料电池驱动器中冷却系统的防冻浓缩物,其提供电导率至多为50μs/cm的即用型含水冷却剂组合物,该浓缩物基于烷撑二醇或其衍生物并含有一种或多种具有2或3个选自氮和硫的杂原子的五元杂环化合物(吡咯衍生物),所述化合物不含或含有至多一个硫原子,并且可以携带稠合芳族的或饱和的六元环。
2.权利要求1的用于燃料电池驱动器中冷却系统的防冻浓缩物,包括总量0.05-5%重量的吡咯衍生物。
3.权利要求1或2的用于燃料电池驱动器中冷却系统的防冻浓缩物,包括苯并咪唑、苯并三唑、甲苯三唑和/或氢化甲苯三唑作为吡咯衍生物。
4.权利要求1-3任一项的用于燃料电池驱动器中冷却系统的防冻浓缩物,其中除吡咯衍生物之外,该浓缩物还含有原硅酸盐,提供了一种硅含量为2-2000ppm重量的即用型含水冷却剂组合物。
5.权利要求1-4任一项的用于燃料电池驱动器中冷却系统的防冻浓缩物,其中使用的烷撑二醇是单乙二醇。
6.权利要求1-5任一项的用于燃料电池驱动器中冷却系统的防冻浓缩物,它在用去离子水稀释时得到电导率至多为50μs/cm的即用型含水冷却剂组合物,所述浓缩物的基本组成是
(a)10-90%重量的烷撑二醇或其衍生物,
(b)90-10%重量的水,
(c)0.005-5%重量的吡咯衍生物,以及
(d)如果需要,原硅酸盐。
7.一种用于燃料电池驱动器中冷却系统的即用型含水冷却剂组合物,其基本组成是:
(a)10-90%重量的烷撑二醇或其衍生物,
(b)90-10%重量的水,
(c)0.005-5%重量的吡咯衍生物,以及
(d)如果需要,原硅酸盐,它是通过用去离子水稀释权利要求1-5任一项的防冻浓缩物而得到的。
8.具有2或3个选自氮和硫的杂原子且不含或含有至多一个硫原子并可以携带稠合芳族或饱和六元环的五元杂环化合物(吡咯衍生物),用于制备在燃料电池驱动器的冷却系统中的、基于烷撑二醇或其衍生物的防冻浓缩物的用途。
9.权利要求8的防冻浓缩物用于制备燃料电池驱动器中冷却系统的电导率至多为50μs/cm的即用型含水冷却剂组合物的用途。
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CN102403520A (zh) * | 2010-09-14 | 2012-04-04 | 铃木株式会社 | 燃料电池系统和燃料电池车辆 |
US8951689B2 (en) | 2010-09-14 | 2015-02-10 | Suzuki Motor Corporation | Fuel cell system including coolant additive and ion exchange resin and fuel-cell vehicle |
CN102403520B (zh) * | 2010-09-14 | 2015-07-29 | 铃木株式会社 | 燃料电池系统和燃料电池车辆 |
CN109762642A (zh) * | 2018-12-29 | 2019-05-17 | 中国船舶重工集团公司第七一八研究所 | 一种低电导冷却液及其制备方法 |
CN109762642B (zh) * | 2018-12-29 | 2021-12-07 | 中国船舶重工集团公司第七一八研究所 | 一种低电导冷却液及其制备方法 |
CN114787288A (zh) * | 2019-12-10 | 2022-07-22 | Kd精细化工有限公司 | 传热流体用着色剂及包含其的组合物 |
CN114787288B (zh) * | 2019-12-10 | 2024-02-13 | Kd精细化工有限公司 | 传热流体用着色剂及包含其的组合物 |
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