CN1140618C - 润滑组合物 - Google Patents

润滑组合物 Download PDF

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Publication number
CN1140618C
CN1140618C CNB998033332A CN99803333A CN1140618C CN 1140618 C CN1140618 C CN 1140618C CN B998033332 A CNB998033332 A CN B998033332A CN 99803333 A CN99803333 A CN 99803333A CN 1140618 C CN1140618 C CN 1140618C
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weight
lubricating composition
composition
phenyl
alkyl
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CNB998033332A
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CN1296521A (zh
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H・莱昂哈德特
H·莱昂哈德特
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Abstract

本发明涉及一种润滑组合物，该组合物包含烃润滑剂基础油与(a)苯基-萘胺、(b)硫代磷酸盐和(c)二苯基胺的组合，优选与(d)天冬氨酸酯组合使用。本发明还涉及该润滑组合物的用途，用于润滑燃气轮机和蒸汽轮机的组合体。

Description

润滑组合物
本发明涉及润滑组合物，更准确地说，涉及用于润滑蒸汽轮机和燃气轮机组合体的润滑组合物。
用于发电的燃气轮机和蒸汽轮机的组合使用有优点，即，它比与任一类型的叶轮机一起发电更有效率。在下文中该组合也称为“组合循环”。润滑一种组合循环的困难在于，必须润滑各种不同的组件，即轴承(轴颈和止推两者)、齿轮、液压控制体系、挠性联轴节和注油轴密封装置。虽然可以润滑每个组件本身，但是有利的是，对于所有零件来说使用单一的普通润滑剂的单一普通润滑体系。
在普通体系中使用的润滑组合物必须满足相当突出的组合要求，以便满意地润滑每个组件。这些要求包括，对于燃气轮机零件的相当苛刻的热-和氧化稳定性要求和严格的起泡量，而蒸汽轮机零件要求该油类有好的脱水性能和极好的耐腐蚀性。高温氧化稳定性是指润滑组合物在高温下形成沉淀物的趋势低、粘性增加低和总酸值增加低。理想的特性是在按照通用电气公司规程GEK 32568 C和GEK 101941中所述进行高温改性并进行氧化稳定性试验DIN 51394之后，粘性增加至多为20％、总酸值增加至多为3.0mg KOH/g和油泥渣含量小于300mg/100ml；优选小于250ml/g，更优选小于200ml/g，最优选小于150ml/g。在确定产生的油泥渣数量时，必须小心地从试验中使用的所有装备中除去该油泥渣。通过过滤从该油中分离出油泥渣。
已经发现，润滑组合物形成油泥渣的趋势对于润滑组合物是否适用于润滑组合循环装备中是重要的。
在组合循环中使用的润滑组合物还必须有一定的粘度指数、倾点、可滤性和抗磨损性能，同时该组合物在许多年之后还应该具有足够的润滑作用。
使润滑油适用于组合循环来达到复合润滑剂性质的组合。
在EP-A-696636中公开了(A)一种润滑基础油、(B)烷基二苯胺和/或苯基-α-萘基胺和(C)硫化钼氧(Oxymolybdenum sulfide)二硫代氨基甲酸盐和/或硫化钼氧有机二硫代磷酸盐(organophosphorodithioate)。可以单独使用一种烷基二苯胺，或可以一起使用两种或两种以上的烷基二苯胺。可以单独使用一种苯基-α-萘胺，或可以一起使用两种或两种以上的苯基-α-萘胺。也可以一起使用一种或一种以上的烷基二苯胺和一种或一种以上的苯基-α-萘胺。在实施例中，使用了单一烷基二苯胺或者单一苯基-α-萘胺。根据该文献，在唯一的实施例中使用了硫化钼氧有机二硫代磷酸盐。EP-A-696636没有公开或者提到使用烷基二苯胺和苯基-α-萘胺与硫代磷酸盐的具体组合物。
而且，已知在用于航空目的的燃气涡轮发动机中使用的酯基础油中，使用了胺类抗氧化剂的组合，它任选与硫代磷酸盐组合使用。在GB-B-990097、GB-A-2272000和GB-B-1293245中，已经描述了此种配方。这些文献没有公开或者提到在烃润滑剂基础油中使用二苯胺、硫代磷酸盐和苯基-α-萘胺的组合物。
现在已经发现，一种润滑组合物满足在组合循环中的使用要求。而且，此润滑组合物在高温下具有特别低的形成油泥渣的趋势。
本发明的润滑组合物包括一种烃润滑剂基础油和如下组分：(a)苯基-萘胺、(b)硫代磷酸盐和(c)二苯胺；其中基础油的80％以上由只由氢和碳组成的化合物组成。
本发明的润滑组合物可以包括每个组份(a)、(b)、(c)和(d)的单一化合物或者这些化合物的混合物。后者是下面讨论的通式I的化合物。
在本发明中使用的苯基-萘胺可以是取代的或者非取代的苯基-萘胺，或者两者的混合物。可以以苯基-萘胺或以其盐的形式使用。优选的取代苯基-萘胺是单烷基化苯基-α-萘胺。更进一步优选的苯基-α-萘胺是单辛基化的苯基-α-萘胺。
该苯基-萘胺优选是一种苯基-α-萘胺。
苯基-萘胺最好是一个非取代的苯基-α-萘胺。在本发明中可以使用市场上可买到的苯基-萘胺。
本发明的润滑组合物还包括一种二苯胺。该二苯胺可以是取代的或者非取代的。优选使用烃基取代的二苯胺，更优选烷基取代了的二苯胺。优选的二苯胺是4，4’-二烷基二苯胺。烷基优选含有2-15个碳原子，更优选含5-12个碳原子。优选的二苯胺是二辛基二苯胺。
硫代磷酸盐化合物可以是硫代磷酸、取代的硫代磷酸、硫代磷酸的盐和/或取代的硫代磷酸的盐。该硫代磷酸盐优选由一个或者多个烃基基团取代，该烃基基团可以任意地含有一个酸基、羟基和/或酯基团。该烃基片断优选包含不超过12个碳原子的烷基。该烃基取代的硫代磷酸盐优选包含2个或者3个烃基基团，或者是包含2个和3个烃基基团的硫代磷酸盐的混合物。
该硫代磷酸盐可以包含许多直接链接到磷原子上的硫原子。该硫代磷酸盐优选是单硫代磷酸盐和/或二硫代磷酸盐。
在本发明中硫代磷酸或者其盐皆可以使用。优选使用硫代磷酸盐。更优选使用硫代磷酸盐的胺盐。在EP-A-375324中已经描述了更优选的硫代磷酸盐和制备它们的方法。市场上可买到的合适的硫代磷酸盐是Lubrizol公司生产的LZ 5125。
在本发明的润滑组合物中存在的烃润滑剂基础油可以是适合于润滑剂使用的任何烃油。不同的合适基础油可以有不同的润滑粘度。烃基础油基本上由只含氢和碳的化合物组成。可以存在有限数量的杂质例如含硫化合物。优选地，基础油的80％(重量)以上，更优选90％(重量)以上由只由氢和碳组成的化合物组成。基础油可以是天然的或者合成的润滑油，或者它们的混合物。天然油可以是矿物油例如煤油，和石蜡烃、环烷烃、或混合的石蜡烃/环烷烃类的、经溶剂处理或者酸处理的矿物润滑油，该矿物润滑油还可以通过加氢裂化和加氢精制方法和/或脱蜡而进一步精制。合成润滑油包括烃油例如聚合-和共聚的烯烃。按照DIN 51378测量，基础油优选地是一种包含小于10重量％、优选小于5重量％，最优选小于3.0重量％的芳族化合物的矿物油。根据ASTMD 4045测量，该基础油还优选包含小于1.0重量％，较优选小于0.1重量％，更优选小于0.05重量％的元素硫。通过严格的加氢处理，可以获得此种矿物油。该润滑剂基础油优选在40℃下具有5-220cSt，更优选10-200cSt，最优选20-100cSt的运动粘度。
本发明的组合物优选不含硫化的脂肪酸。硫化的脂肪酸数量优选为小于0.5重量％，以润滑组合物的总量为基准计，更优选小于0.1重量％，最优选小于0.02重量％，以组合物的总量为基准计。
本发明的润滑组合物任选地包括下列通式I化合物所示的另一种组分(d)： (通式I)
其中R1和R2各为氢或有1-30个碳原子的烷基或羟基烷基；R3、R4和R5各为氢或有1-4个碳原子的烷基或羟基烷基，X是CH或N，而R6和R7各为氢、有1-30个碳原子的烷基或烯基，或由不超过30个碳原子的饱和或不饱和的羧酸衍生的酰基基团。优选地，R1和R2各为3-6个碳原子的烷基，R3、R4和R5各为氢，X是N，而R6和R7各为有15-20个碳原子的烷基或者由包含4-10个碳原子的饱和或不饱和的二羧酸衍生的酰基，R6和R7至少一个是酰基基团。特别优选的是天冬氨酸、N-(3-羧基-1-氧代-2-丙烯基)-十八烷基-双(2-甲基丙基)酯。这样的天冬氨酸酯是市场上可买到的。
本发明的润滑组合物优选不包含显著量的酚类抗氧化剂。已经发现，在高温下使用酚类抗氧化剂，更准确地说使用烷基化苯酚例如2，6-二-叔丁基-酚和4，4’(亚甲基双(2，6-二-叔丁基-酚))会增加油泥渣生成。而且，已知低分子量酚类抗氧化剂有助于蒸发。这导致残余的润滑组合物失效。存在的酚类抗氧化剂数量优选小于1重量％，更优选小于0.5重量％，最优选小于0.1重量％，以组合物总量为基准计。
该润滑组合物还可以包含传统的添加物。该组合物最好还包含金属减活剂、防锈剂、抑泡剂和/或破乳剂。组分(d)是优选的防锈剂。
存在于润滑组合物的添加物数量取决于使用的具体化合物。
通常，该润滑组合物优选包含0.1-5.0重量％、优选0.2％-2.0％的苯基-萘胺，0.01-1.0重量％、优选大于0.02％且优选少于0.5％的硫代磷酸盐，0.1-5.0重量％、优选大于0.2％且优选少于2.0％的二苯基胺，0-1.5重量％、优选0-1.0重量％的通式I化合物；和至少95重量％的基础油，优选矿物油，所有的含量都是以该组合物的总量为基准计。
本发明还涉及本发明润滑组合物的用途，用于润滑燃气轮机和蒸汽轮机的组合体，更优选用于增压-蒸汽发电机的组合体。而且，本发明涉及利用燃气轮机和增压-蒸汽发电机的蒸汽轮机组合体的润滑。
将苯基-萘胺、硫代磷酸盐、二苯胺、烃基础油和任选的通式I的化合物加在一起，可以制备本发明的润滑组合物。
实验
根据在通用电气规范GEK 32568C和GEK 101941中所述的高温改性方法，已经对多个配方进行了高温氧化稳定性试验，被称为氧化试验DIN 51394。在此试验中，在五种金属催化剂(铜、钢、铝、镁、银)参与的情况下，将油保持在175℃下72小时，同时空气以3升/小时的速度通过油中鼓泡。在试验结束时，分析油的粘度增加、总酸值增加和产生的油泥渣总量。必须小心地从该装备、特别是从全高度的汽缸旁边除去油泥渣。通过借助于从Millipore买到的5微米过滤纸过滤分离出油泥渣，用正庚烷冲洗移出的油泥渣，接着干燥并称重。
这些配方包含下列添加物。
胺式抗氧化剂I：苯基-α-萘胺(未取代的)
胺式抗氧化剂II：二辛基二苯基胺
防锈剂：天冬氨酸、N-(3-羧基-1-氧代-2-丙烯基)-N-十八烷基，双(2-甲基丙基)酯。
抗磨添加剂：二烷基硫代磷酸盐的胺盐，从Lubrizol可买到的LZ5125。
将添加物加入到一种包含一种溶剂提取了的和加氢精制了的矿物油的基础油中，该矿物油含小于3重量％的芳族化合物(通过DIN 51378测量)和小于0.05重量％的硫化合物(通过ASTM D4045测量)，以元素硫计算，并且还含传统的金属减活剂、抑泡剂和破乳剂。对于组合物1和2来说，使用基础物流体A。对于组合物3-5来说，使用基础物流体B。这些流体在存在的传统金属减活剂方面不同。
含量是占包括矿物油在内的配方总量的重量％。
                                          组合物
  1   2(对比)   3   4(对比)   5(对比)
  基础物流体   A   A   B   B   B
  胺式抗氧化剂I   0.5   0.5   0.5   1.0   -
  胺式抗氧化剂II   0.5   0.5   0.5   -   1.0
  抗磨添加剂   0.1   -   0.1   0.1   0.1
  防锈剂   0.1   0.1   0.1   0.1   0.1
  油泥渣形成(mg/100ml)   190   360   144   234   352

Claims (7)

1.一种润滑组合物，包含烃润滑剂基础油和如下组分：
(a)苯基-萘胺，
(b)硫代磷酸盐，和
(c)二苯基胺，
其中基础油的80％以上由只由氢和碳组成的化合物组成。
2.根据权利要求1的润滑组合物，其组合物还包含
(d)下列通式I化合物：
Figure C9980333300021
 (通式I)
其中R1和R2各为氢或有1-30个碳原子的烷基或羟基烷基；R3、R4和R5各为氢或有1-4个碳原子的烷基或羟烷基；X是CH或N；而R6和R7各为氢、有1-30个碳原子的烷基或烯基、或由不超过30个碳原子的饱和或不饱和的羧酸衍生的酰基基团。
3.根据权利要求1或2的润滑组合物，其组合物包含少于0.02重量％的硫化脂肪酸。
4.根据权利要求1-3中任何一个的润滑组合物，其组合物含有作为基础油的矿物油，该矿物油含有小于10重量％的芳族化合物和小于1.0重量％的硫，以元素硫计算。
5.根据权利要求1-4中任何一个的润滑组合物，该润滑组合物还包含金属减活剂、防锈剂、抑泡剂和/或破乳剂。
6.根据权利要求1-5中任何一个的润滑组合物，该组合物包含0.1-5.0重量％的苯基-萘胺、0.01-1.0重量％的硫代磷酸盐和0.1-5.0重量％的二苯基胺，0-1.5重量％的通式I化合物，和至少95重量％的矿物油，所有的百分比都以该组合物的总量为基准计。
7.根据权利要求1-6中任何一个的润滑组合物的用途，用于润滑燃气轮机和蒸汽轮机的组合体。
CNB998033332A 1998-02-27 1999-02-24 润滑组合物 Expired - Lifetime CN1140618C (zh)

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