CN102137919A - 液压流体和防止蒸气腐蚀的方法 - Google Patents

液压流体和防止蒸气腐蚀的方法 Download PDF

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CN102137919A
CN102137919A CN2009801350917A CN200980135091A CN102137919A CN 102137919 A CN102137919 A CN 102137919A CN 2009801350917 A CN2009801350917 A CN 2009801350917A CN 200980135091 A CN200980135091 A CN 200980135091A CN 102137919 A CN102137919 A CN 102137919A
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glycol
hydraulic fluid
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S·哈米德
L·E·施米德特克
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BASF Corp
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Abstract

公开了具有蒸气相腐蚀抑制性能的基于金属二醇的液压流体。该液压流体可被用于食物相关的应用。

Description

液压流体和防止蒸气腐蚀的方法
相关申请的交叉引用
本申请要求2008年8月28日提交的美国临时专利申请61/092,483的权益,其全盘引入本文作为参考。
技术领域
本发明涉及基于水-二醇(W/G)的液压流体和防止归因于使用基于W/G的液压流体的蒸气相腐蚀。更具体地说,本发明涉及基于W/G的液压流体,其包含铵盐作为蒸气相腐蚀抑制剂。液压流体可被用于各种实际应用,包括食物相关的应用。
背景技术
液压流体用作用于各种实际应用的动力传送介质。这些液压流体必须满足严格的性能标准,如热稳定性、耐火性、在宽温度范围内对粘度变化的低敏感性、良好的水解稳定性和良好的润滑性。
若干液压流体基于矿物油。这些基于烃的流体满足性能标准,并且没有造成严重的腐蚀问题,因为该流体基本上没有水。然而,基于烃的液压流体确实造成了潜在的火灾危险。若干目前的液压流体因此基于水-二醇混合物,其克服了火灾忧虑,但金属部件的腐蚀变成了显著的问题。
基于W/G的液压流体包含大量的水。一些流体中的水含量可以最高达60重量%,和典型地为至少35重量%。在流体中存在高百分比的水,当在液压系统中并且在空气/氧气的存在下被加热到150℉或更高的操作温度时,产生了由非不锈钢或铸铁制成的金属部件的腐蚀的理想条件。
各种添加剂被包括在基于W/G的液压流体中以便抑制金属部件的腐蚀。例如,吗啉及其它烷基烷醇胺已经在工业、非食物相关的应用中用作蒸气相腐蚀抑制剂。然而,仍然需要在基于W/G的液压流体,特别地用于食物相关的应用的基于W/G的液压流体中包括有用的无机蒸气相腐蚀(VPC)抑制剂。目前,没有为基于W/G的液压流体而设计的商品化VPC抑制剂满足食品与药物管理局(FDA)用于食物相关的应用的要求。
发明内容
本发明涉及基于W/G的液压流体,其抑制暴露的金属表面的蒸气相腐蚀。更具体地说,本发明涉及基于W/G的液压流体,其包括铵盐作为VPC抑制剂。本发明的流体适用于食物相关的应用。用于食物相关的应用中的现有的基于W/G的液压流体不包含VPC抑制剂,并且因此缺乏重要的作业性能。本发明的基于W/G的液压流体克服了这个未解决的问题。
因此,本发明的一个方面提供基于W/G的液压流体,其抑制由液压流体的气化引起的暴露的金属表面的腐蚀。本发明的基于W/G的液压流体包括铵盐作为VPC抑制剂。
本发明的又一方面提供抑制、延迟或防止由液压流体引起的暴露的金属表面的蒸气相腐蚀的方法,包括在基于W/G的液压流体中引入有效量的例如约0.05重量%至约1重量%的铵盐。
本发明的另一方面提供基于W/G的液压流体,其包括:
(a)约25重量%至约50重量%的二醇;
(b)约0.5重量%至约8重量%的部分中和的脂族C6-C16羧酸;
(c)约15%重量至约40重量%的聚亚烷基二醇;
(d)约0.05重量%至约1重量%的铵盐;
(e)足够量的缓冲碱以便提供至少约20ml的储备碱度;
(f)总计0重量%至约0.5重量%的消泡剂、染料和金属钝化剂的一种或多种;和
(g)约25%至约50重量%的水。
本发明的另一方面提供具有至少约20ml的储备碱度的基于W/G的液压流体,以便延长所述液压流体的使用寿命。
本发明的这些及其它方面将由以下优选实施方案的详细描述变得明显。
附图说明
图1包含暴露于对比的基于W/G的液压流体的蒸气(左侧)或本发明的包含铵盐的基于W/G的液压流体的蒸气(右侧)的铸铁板的照片。
具体实施方式
本发明涉及基于W/G的液压流体。基于W/G的流体被广泛使用,因为它们是耐火的。本发明的基于W/G的液压流体可被用于各种实际应用,特别地包括食物相关的应用。根据本发明的重要特征,暴露的金属表面在提高的操作温度下抵抗由基于W/G的液压流体的蒸发所引起的蒸气相腐蚀。
本发明的基于W/G的液压流体抑制、延迟和/或防止暴露的金属表面的腐蚀。当相比于由不含或基本上不含铵盐的相同的基于W/G的液压流体引起的相同金属的直观氧化的量,金属表面直观上被包含铵盐的基于W/G的液压流体的蒸气较少氧化时,金属表面的腐蚀被抑制、延迟或防止。
“基本上不含”铵盐的基于W/G的液压流体包含小于约0.05重量%的铵盐。使用本发明的组合物和方法,各式各样的金属表面的腐蚀可以被抑制、延迟或防止。例如,在金属表面,包括但不限于铁、钛、铝、铜、锌、镍、钴、铬、镁和其它金属上可以抑制腐蚀。本发明的组合物和方法也可用于保护合金,例如但不限于钢。
本发明的基于W/G的液压流体包括:
(a)约25重量%至约50重量%的二醇;
(b)约0.5重量%至约8重量%的部分中和的脂族C6-C16羧酸;
(c)约15重量%至约40重量%的聚亚烷基二醇;
(d)约0.05重量%至约1重量%的铵盐;
(e)足够量的缓冲碱以便提供至少约20ml的储备碱度;
(f)总计0重量%至约0.5重量%的消泡剂、染料和金属钝化剂的一种或多种;和
(g)约25重量%至约50重量%的水。
本发明的液压流体适用于各种实际应用,包括食物相关的应用。本发明的基于W/G的液压流体抑制、延迟和/或防止归因于使用这些液压流体的暴露的金属表面的蒸气相腐蚀。
本发明的重要特征是在食物相关的应用中使用本发明的液压流体的能力。目前,FDA没有批准商品化VPC抑制剂以便防止源于使用液压流体的VPC。在广泛研究后,发现合适的腐蚀抑制剂也可被用于偶然食品接触润滑剂中所用的组合物(21 C.F.R.§178.3570)。
本发明的液压流体包括约25重量%至约50重量%的二醇。在优选实施方案中,本发明的液压流体包括约30重量%至约45重量%,和更优选地约35重量%至约40重量%的二醇。二醇被包括在组合物中作为防冻剂和稀释剂,并且用于提供一定的粘度控制。二醇可以是例如乙二醇、丙二醇、丁二醇、戊二醇、己二醇、二甘醇、双丙甘醇、一缩二己二醇、三甘醇、二缩三丙二醇、二缩三己二醇和其混合物。也可以使用其它类似的二醇。
本发明的液压流体还包含约0.5重量%至约8重量%,和优选地约1重量%至约6重量%的部分中和的脂族C6-C16直链或支链羧酸。部分中和的C6-C16羧酸用作边界润滑剂以便改善基于W/G的液压流体的性能,特别是耐磨性和污泥溶解性。
例如,脂族C6-C16羧酸可以是己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十一烷酸、十四烷酸、十五烷酸、十六烷酸、十三烷酸、2-乙基己酸和2-丙基己酸中的一种或多种。优选的C6-C16羧酸包含六至十个碳原子。中和剂以足以中和C6-C16羧酸的羧基中的至少一部分的数量被添加到基于W/G的流体中。
脂族C6-C16羧酸用中和剂中和,典型地为碱金属氢氧化物,如氢氧化钠、氢氧化钾、氢氧化锂或其混合物。优选的中和剂是氢氧化钾。中和剂以足以中和至少约50%,和优选地至少约60%,和最高达约99%,但小于100%的C6-C16羧酸的羧基的数量添加。
本发明的基于W/G的液压流体还包含约15重量%至约40重量%的聚亚烷基二醇。在优选实施方案中,聚亚烷基二醇以占流体约20重量%至约30重量%的数量存在。聚亚烷基二醇用作增稠剂以提供期望的粘度。
聚亚烷基二醇的身份不受限制,并且若干商品化聚亚烷基二醇可用于本发明的基于W/G的液压流体。聚亚烷基二醇典型地是EO与PO的比值为约10∶1至约1∶10的环氧乙烷(EO)和环氧丙烷(PO)的共聚物。EO和PO的均聚物,即聚乙二醇和聚丙二醇,也可被用作聚亚烷基二醇。聚亚烷基二醇的分子量例如为至少约5,000,典型地超过约10,000,最高达约200,000。一种聚亚烷基二醇或聚亚烷基二醇的混合物可被用于本发明的基于W/G的液压流体。
可用于本发明的基于W/G的流体的一类商品化的聚亚烷基二醇是PLURASAFE
Figure BPA00001328950900041
产品,可获自BASF Corp.,Floral Park,NJ。有用的PLURASAFE
Figure BPA00001328950900042
产品的实例是PLURASAFE
Figure BPA00001328950900043
WT 90000H,一种包含60重量%的具有环氧乙烷的甲基-环氧乙烷聚合物(CAS号9003-11-6)和40重量%水的组合物。PLURASAFE
Figure BPA00001328950900051
WT 90000H被批准用于偶然食品接触。其它有用的PLURASAFE
Figure BPA00001328950900052
产品是WS-660、WS-2000、WS-5100、WT-1400、WT-9150和WT-150,000。这些PLURASAFE产品中的每一个被批准用于偶然食品接触。
根据本发明的重要特征,本发明的基于W/G的液压流体包括足够数量的铵盐以便抑制、延迟和/或防止暴露于基于W/G的液压流体的蒸气的金属表面的蒸气相腐蚀。典型地,基于W/G的流体包含约0.05重量%至约1重量%的铵盐。在优选实施方案中,基于W/G的流体包含约0.1重量%至约0.8重量%,和更优选地,约0.15重量%至约0.6重量%的铵盐。
铵盐的身份不受特别地限制。然而,铵盐必须是以添加到液压流体的量水溶性的并且必须允许在操作温度下氨的气化以便保护暴露的金属表面免受VPC的破坏。合适的铵盐包括但不局限于氢氧化铵、碳酸铵、乙酸铵和其混合物。这些铵盐中的每一种被批准作为用于人消费的食品添加剂。
本发明的基于W/G的液压流体的另一组分是足够量的缓冲碱以便提供至少约20ml的储备碱度。液压流体磨损性能直接与流体pH有关,并且因此pH被维持在足够高的值。缓冲碱控制液压流体的储备碱度、pH和酸度。储备碱度是以滴定100ml的基于W/G的液压流体至pH 5.5所需要的0.1M盐酸的体积(单位毫升)报道的。
在优选实施方案中,存在足够量的缓冲碱以便提供至少约22ml,和更优选地至少约25ml的残余碱度,至多约35ml的储备碱度。在这种储备碱度水平下,基于W/G的流体的使用寿命具有足够的缓冲能力以便保持流体的pH值约等于或高于约9,例如,约10至约12,并且避免大的快速的pH波动。优选地,液压流体的pH值被维持在约9至约11。有用的缓冲碱因此包括但不局限于碳酸盐、碳酸氢盐、硼酸盐、四硼酸盐、磷酸盐和其混合物。缓冲碱例如可以以钠或钾盐的形式添加。
本发明的基于W/G的流体进一步包括任选的液压流体领域技术人员已知的成分。这些任选的成分包括消泡剂、用于泄漏检查的染料和用于防止与液体基于W/G的液压流体接触的金属腐蚀的金属钝化剂。这些任选的成分以总计占流体0重量%至约0.5重量%的数量存在。合适的金属钝化剂包括可获自CIBA的IRGAMET类型的金属钝化剂,如IRGAMET
Figure BPA00001328950900061
30、39、42、BTZ和TTS。消泡剂典型地是基于硅氧烷的消泡剂。
基于W/G的液压流体的载体是水,其以占流体约25重量%至约50重量%的数量存在。水优选地是去离子(DI)水,因为存在于饮用水中的钙和镁离子可以与流体添加剂反应,引起形成絮状物或沉淀物,从而不利地影响流体性能。为延长流体和元件寿命,W/G-液压流体中所包括的水的最大总硬度应为百万分之五份(ppm)。
本发明的组合物通过简单地混合组合物成分直到提供均质溶液来制备。典型地,预混合水、碱金属氢氧化物(例如氢氧化钾)和碳酸铵,随后添加C6-C16羧酸。这种添加典型地继之以添加二醇和聚亚烷基二醇,随后添加全部剩余的液压流体成分。
为证明本发明的基于W/G的液压流体,和其抑制、延迟和/或防止暴露的金属表面受VPC的腐蚀的能力,制备以下液压流体并且测试腐蚀抑制。
对比例(现有技术)
这个对比例不含VPC抑制剂,并且类似于目前市售的基于W/G的液压流体
实施例
Figure BPA00001328950900071
1)典型地碳酸铵、氢氧化铵、乙酸铵或其混合物,基于100%活性基准。
所测试的铵盐是氢氧化铵、乙酸铵和碳酸铵。每一种铵盐被列为人消费用的食品添加剂。使用一种基于W/G的液压流体,即,上述典型实例,其包含0.5重量%氢氧化铵、约40重量%丙二醇、约22.5重量%PLURASAFEWT-90,000H、约0.2重量%碳酸钠和约3.5重量%部分中和的癸酸,进行第一次测试。该腐蚀抑制测试利用悬挂在圆柱形缸中的100ml的液压流体上面的三个铸铁板。缸的顶部覆盖有软木塞,其具有用于冷凝管的开口。将缸置于设定在150℉的恒温浴中,并且加热样品96小时。目测铸铁板的生锈和腐蚀情况。在任何板上没有观察到可见的腐蚀。使用对照缸,其包含相同的液压流体,但不包含氢氧化铵(例如对比例1),的单独的测试导致在全部三个铸铁板上的严重的生锈。
使用包含碳酸铵或乙酸铵的基于W/G的液压流体,重复这个测试。在任一个测试中,在任何铸铁板上,没有观察到腐蚀。
图1图示说明了本发明的、市售可得的基于W/G的液压流体的腐蚀抑制效果。在左边的铸铁板的照片显示出显著的蒸气相腐蚀,而在右边的铸铁板没有蒸气相腐蚀。在左边的板经受了不含铵盐的基于W/G的液压流体的蒸气,而在右边的板经受了相同的但包含0.5重量%氢氧化铵的基于W/G的流体的蒸气。
目前,没有商品化的基于W/G的液压流体适于食品-相关的应用,因为不能得到用于这样的流体的食品级VPC添加剂。在测试作为VPC抑制剂的批准用于直接食品添加剂的各种化合物中,发现仅仅铵盐提供了足够的VPC保护,如下表1中所示。
表1
在145℉的蒸气相腐蚀测试
Figure BPA00001328950900081
1)来自上述的典型的对比例
表1表明不包含VPC抑制剂,或包含亚硝酸钠或碳酸钠的液压流体不能通过48小时或96小时的VPC测试。亚硝酸钠通过了24小时测试,但该时间长度不满足于实际的流体应用。包含氢氧化铵、乙酸铵或碳酸铵的液压流体每个都通过了96小时VPC测试。这种VPC抑制至少部分地归因于氨的挥发,这赋予了暴露的金属表面的VPC抑制。使用标准腐蚀抑制剂,如苯并三唑和聚季铵化合物,的测试不能赋予VPC抑制,因为在液压流体的操作条件下这样的化合物不是挥发性的。
为进一步改善本发明的基于W/G的液压流体的性能,通过添加缓冲碱将储备碱度增加到大于20ml。储备碱度对于增加流体的使用寿命是重要的。具有低储备碱度的液压流体在较短的时间段内开始显示出高磨损。
在这个测试中,将碳酸钠(0.5重量%)添加到包含0.25重量%碳酸铵的基于W/G的液压流体中。添加碳酸钠将储备碱度从15ml增加到22.5ml。在150℉,和1500和1750psi的标准条件下操作基于W/G的液压流体。使用ASTM D2882的程序进行的泵测试显示出平均磨损,一次重复测试小于70mg磨损。ASTM D2882测试是在Sperry Vickers V-104C叶轮泵中在2,000psi(13.8MPa)达100小时并且以8加仑/分钟(30.6L/min)进行的。

Claims (14)

1.液压流体,其包括:
(a)约25重量%至约50重量%的二醇;
(b)约0.5重量%至约8重量%的部分中和的脂族C6-C16羧酸;
(c)约15重量%至约40重量%的聚亚烷基二醇;
(d)0.05重量%至约1重量%的铵盐;
(e)足够量的缓冲碱以便提供至少约20ml的储备碱度;
(f)总计约0重量%至约0.5重量%的消泡剂、染料和金属钝化剂的一种或多种;和
(g)约25重量%至约50重量%的水。
2.权利要求1的流体,其中二醇选自乙二醇、丙二醇、丁二醇、戊二醇、己二醇、二甘醇、双丙甘醇、一缩二己二醇、三甘醇、二缩三丙二醇、二缩三己二醇和其混合物。
3.权利要求1的流体,其中C6-C16羧酸包括己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十一烷酸、十四烷酸、十五烷酸、十六烷酸、十三烷酸、2-乙基己酸和2-丙基己酸中的一种或多种。
4.权利要求1的流体,其中C6-C16羧酸被中和至少50重量%至小于100重量%。
5.权利要求1的流体,其中聚亚烷基二醇包括聚乙二醇、聚丙二醇、环氧乙烷-环氧丙烷共聚物或其混合物。
6.权利要求1的流体,其中聚亚烷基二醇具有最小约5000和最高达约200,000的分子量。
7.权利要求1的流体,其中聚亚烷基二醇包括甲基-环氧乙烷聚合物。
8.权利要求1的流体,其中铵盐是碳酸铵、氢氧化铵和乙酸铵中的一种或多种。
9.权利要求1的流体,其中缓冲碱选自碳酸盐、碳酸氢盐、硼酸盐、四硼酸盐、磷酸盐和其混合物。
10.传送动力或携带负载的方法,其包括使权利要求1的液压流体经受压力。
11.权利要求9的方法,其中在食品加工设备、食品制备设备或食品供应设备中动力被传送或者负载被携带。
12.抑制、延迟或防止由液压流体引起的暴露的金属表面的蒸气相腐蚀的方法,其包括在基于水/二醇的液压流体中引入有效量的铵盐。
13.权利要求12的方法,其中基于水/二醇的液压流体包括约0.5重量%至约1重量%的铵盐。
14.权利要求12的方法,其中基于水/二醇的液压流体包括:
(a)约25重量%至约50重量%的二醇;
(b)约0.5重量%至约8重量%的部分中和的脂族C6-C16羧酸;
(c)约15重量%至约40重量%的聚亚烷基二醇;
(d)0.05重量%至约1重量%的铵盐;
(e)足够量的缓冲碱以便提供至少约20ml的储备碱度;
(f)总计约0重量%至约0.5重量%的消泡剂、染料和金属钝化剂的一种或多种;和
(g)约25重量%至约50重量%的水。
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CN111321030A (zh) * 2018-12-13 2020-06-23 中国石油天然气股份有限公司 食品级含水溶性聚合物难燃液压液组合物

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