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CN101952402B - 替代使用低硫柴油燃料时失去的硫润滑作用的通用合成润滑剂,方法和由方法得到的产品 - Google Patents

替代使用低硫柴油燃料时失去的硫润滑作用的通用合成润滑剂,方法和由方法得到的产品 Download PDF

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Publication number
CN101952402B
CN101952402B CN200780102356.4A CN200780102356A CN101952402B CN 101952402 B CN101952402 B CN 101952402B CN 200780102356 A CN200780102356 A CN 200780102356A CN 101952402 B CN101952402 B CN 101952402B
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mixture
weight
accounts
solvent
fuel dope
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CN101952402A (zh
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R·J·斯隆
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BestLine International Research Inc
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BestLine International Research Inc
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Abstract

本发明公开了一种柴油燃料润滑剂作为超低硫和低硫柴油燃料中的硫润滑的替代品，生产所述润滑剂的方法，以及使用所述润滑剂的方法。该润滑剂含有α-烯烃；低气味芳烃溶剂；和至少一种选自由加氢异构化高级基础油和HT剧烈加氢裂化基础油组成的基础油组中的基础油；以及其它成分。还公开了一种生产这种润滑剂的方法。

Description

替代使用低硫柴油燃料时失去的硫润滑作用的通用合成润滑剂,方法和由方法得到的产品
技术领域
本发明涉及替代合成润滑剂的开发中的最新技术以适应超低硫和低硫柴油燃料中硫含量的显著降低。 
背景技术
在过去几年间，柴油燃料一直遭受环境压力以使润滑要素(硫)大幅降低或消除。在柴油发动机的燃料系统内，硫对于润滑机械部件起主要作用。自2006年10月15日，EPA提出了除加利福尼亚和偏远的阿拉斯加外，美国出售的上路柴油燃料的硫含量的新标准是超低柴油燃料仅限含15PPM的硫。自2006年9月1日，加利福尼亚就已经实行该标准，偏远的阿拉斯加在2010年之前也将使所有柴油转换为超低硫柴油。新规定适用于所有的柴油燃料和柴油燃料添加剂及所掺混的馏分燃料，并且适用于上路使用的柴油，例如煤油。到2010年12月1日，所有公路柴油都将为超低硫柴油。非道路用柴油在2007年将转换为500PPM的硫(低硫柴油)且到2010年将转换为超低硫柴油。在2007年火车和船只柴油也将转换为500PPM的硫，且到2012年转换为超低硫柴油。在1993年10月之前，柴油燃料中的硫含量为5000PPM，这使得可以对运动部件例如燃料泵、喷射器和阀等具有足够的润滑。随着硫的显著降低，减少了必要润滑减少从而使得过早磨损成为柴油机械工业中的一个大问题。 
发明内容
本发明公开了一种作为超低硫和低硫柴油燃料中硫润滑的替代品的柴油燃料润滑剂，生产所述润滑剂的方法，以及使用所述润滑剂的方法。该润滑剂含有α-烯烃、低气味芳烃溶剂、和至少一种选自由加氢异构化高级基础油和HT剧烈加氢裂化基础油组成的基础油组中的基础油、以及其它成 分。还公开了一种生产这种润滑剂的方法。 
具体实施方式
本发明涉及一种替代柴油燃料润滑添加剂用于超低硫和低硫柴油的用途，其可以加入到燃料中替代通常与柴油燃料中较高硫含量相关的润滑作用的显著降低。该产品可用于硫为内部润滑所必需的组分的所有形式的柴油发动机和汽轮机中。本发明已经通过秘密公开提交给EPA，且在2007年10月按照40CFR79.23收到注册号。 
以前的柴油燃料添加剂依赖于柴油燃料中的高浓度硫用量，现在这已受到美国环境保护署和各个国外政府的严格限制。对于新的国际环境标准，柴油中的硫对于上路应用被限制为15PPM。在某些船只和火车运输中，在向超低硫柴油过渡的过程中批准了有限时间的500PPM。 
主要成分 
成品(本发明的优选实施方案)是以下成分的组合： 
●α-烯烃：这是一种主要成分，其也称作烯烃，聚合氯化石蜡液体，和氯化石蜡，其碳链长度为12-24，氯的重量百分数为21.4％-70％，HCl为4-10ppm以及分子量为273.5-650，以及Cl(2)重量分数为20-70％，在25℃下的比重为1.050-1.50，并且HCL的JQD重量百分数为0.20-0.60。该成分的主要用途是用于润滑剂配方、润滑剂添加剂化合物、极压添加剂配方和金属加工化合物。此外α-烯烃及其相关产品减少了老化或水分过度积累时燃料中藻类的生长且使燃料长时间稳定，并同时为燃料系统和发动机的燃烧室提供极度润滑。这提供了超低硫柴油中所缺乏的润滑作用。 
●低气味芳烃溶剂：这是主要成分，其是一种高度精制的低毒、低气味溶剂，理想地用于涂漆、清漆、食品级涂料、粘合剂、稀释剂、冲淡剂、农用化学品、家用杀虫剂、喷淋油和专用化学品。芳烃百分数为5-40％(EC-A-G04)，闪点为20到80℃(ASTM D-93)且30℃(+/-)下密度为0.600-0.900(ASTM D-4052)。 
●加氢异构化高级基础油和HT剧烈加氢裂化基础油：这种主要成分是一种具有低的或没有芳香烃和杂质的剧烈加氢裂化或加氢异构化基础油，其通过原料与氢气发生化学反应以减少或去除含硫、氮和氧的极性化 合物并且将芳香烃转化为饱和环烷烃，从而将重的多环石蜡分子分裂为轻的饱和烃而得到。这可以包括经加氢精制或加氢精炼的馏分油。该基础油可做润滑油、发动机油、切削油、食品加工、药物、工业、农业润滑剂和极压添加剂的主体。这些加入到超低硫柴油燃料的润滑中。 
其它成分 
●十六烷值促进剂、清洁剂、浊点和蜡降低剂混合物：根据本发明，这是一种混合物，其含有建议百分数为10-30重量％且CAS号为27247-96-7的2-乙基己基硝酸酯，所述2-乙基己基硝酸酯是该混合物的主要成分。所建议的石脑油的百分数为50-70重量％且CAS为64742-94-5。所建议的萘的百分数为5-7重量％且CAS号为91-20-3。所建议的三甲基苯的百分数为1-7重量％且CAS号为25551-13-7。这组化合物在掺混到一起时净化并维持发动机的燃烧室，提高燃料的英制热量单位并降低燃料内蜡结晶的团聚。 
●合成磺酸钙：TBN为100-600的高碱值合成磺酸钙，其主要目的是用于极压添加剂配方，从而在铁类金属和有色金属的油溶性添加剂中提供腐蚀保护、分散剂以及清洁性，最小钙重量为10.00-20.00％，总碱数为200-600mg KOH/g(ASTM D-2896)，并且平均分子量(ASTM d-3712)为800-1200。重要提示：在2007年12月，一项新的美国法律颁布，其可能限制未来磺酸钙在燃料添加剂中的应用，所以至少在美国可能必须从本发明中省去该成分。由于上述2-乙基己基硝酸酯提供了类似的腐蚀保护、分散和清洁功能，所以这是可能的。 
●低闪点溶剂油：称作Stoddard溶剂和/或白色溶剂油，且通常用作家用或商用的萃取溶剂、清洗溶剂、气溶胶中的溶剂、涂漆、天然漆、清漆和涂料冲淡剂，并且用最多40％的C7-C12饱和脂肪烃和脂环烃混合物进行加氢脱硫溶剂萃取。闪点为15-40℃，苯胺点为50-80℃，蒸气密度为3.5-6.0(空气为1)和粘度(cps，25℃)为0.70-1.75。作为清洗溶剂，它清除燃料系统中的组分。 
●溶剂活化染料：它们通常用于鉴别燃料和润滑剂的等级或标明用途。它们以粉末和液体两种形式生产，且当引入产品中时是稳定的并给产品留下可识别的颜色。 
●降凝剂或浊点降低剂：它们用于减少石蜡化合物例如润滑剂和柴油 燃料中蜡结晶的聚集或团聚。 
●异构体重整油：也称作溶剂，甲苯，甲基苯以及苯基甲烷，化学式为C7H8(C6H5CH3)且CAS号为108-88-3，分子量为90.00-95.00g/mol和比重为0.800-0.900(水为1)。该化学品为芳香烃，广泛用作工业原料以及用作清洗发动机的燃料系统、储存箱和燃烧室的溶剂。 
●二甲基酮：也称作丙酮。它是无色的，具有低沸点，且与水、醇、大多数烃和其它有机液体，包括柴油燃料原料，混溶从而有助于清洁和减少阀门和活塞顶端积累的碳。 
优选的混合比例 
每种组分优选的混合比例如下所示。重要的是维持混合物中的组分落入下面百分数内。应注意的是，在一种或多种如下所示的成分从柴油润滑添加剂中省去的情况下，剩余成分的重量百分数按比例增加： 
α-烯烃：5-30重量％，优选7.0-25重量％，并且更优选9.0-18重量％。最优选为11.0重量％。 
低气味芳烃溶剂：3.0-27重量％，优选5.0-22重量％并且更优选7.0-18重量％。最优选为15.0重量％。 
加氢异构化高级基础油和HT剧烈加氢裂化基础油：0.50-15重量％，优选0.75-10重量％并且更优选2.0-8.0重量％。最优选为5.0重量％。 
十六烷值促进剂、清洁剂、浊点和蜡降低剂混合物：0.03-0.25重量％，优选0.05-0.20％并且更优选0.09-0.17重量％。最优选为0.13重量％。 
合成磺酸钙：0.05-0.25重量％，优选0.07-0.20重量％并且更优选0.10-0.18重量％。最优选为0.12重量％。 
低闪点溶剂油：15-50重量％，优选20-45重量％并且更优选25-39重量％。最优选为35重量％。 
溶剂活化染料：0.002-0.005重量％，优选0.0025-0.004重量％并且更优选0.027-0.035重量％。最优选为0.003重量％。 
降凝剂或浊点降低剂：0.50-2重量％，优选0.65-1.75重量％并且更优选0.75-1.35重量％。最优选为1重量％。 
异构体重整油：0.50-5.0重量％，优选0.75-4.0重量％并且更优选1.0-3.0重量％。最优选为2.0重量％。 
二甲基酮：10-50重量％，优选17-40重量％并且更优选24-36重量％。最优选为30重量％。 
优选的组分掺混顺序 
初始掺混(主要掺混)需要将α-烯烃、低气味芳烃溶剂和基础油掺混直到液体均匀混合而没有出现任何分离。掺混是基于搅拌器的速度且温度将指示完成掺混的时间。掺混时间可为4到6小时。对于理想的掺混，每种组分的理想温度为22-30℃。在该掺混时，可在较小的高速密闭混合器中准备十六烷值促进剂、清洁剂、浊点和蜡降低剂的第二掺混物，然后加入到主掺混物中。 
如果使用合成磺酸钙(注意现今美国法律可能限制它们在美国的使用)，在掺混的初始阶段，需要合成磺酸钙以约50/50的比例与溶剂油掺混产生第三混合物。(所用的溶剂油将为上述优选的百分数。)然后可将该第三混合物，或无合成磺酸钙时单独的溶剂油，连同余量成分，加入到主混合物中，并且运行搅拌器直到各组分看起来已经完全掺混为均匀液体。 
优选的掺混设备 
该工艺顺序涉及一系列的掺混和容纳罐，在容纳罐里可将产品称重并随后泵送通过控制阀以维持一致的流量和压力。掺混应该在密闭罐中进行以减少产品蒸发(损失)并防止直接暴露于火花。掺混设备可以是高速或低速掺混设备的组合。容纳罐的尺寸和体积对掺混来说并不关键。 
本发明的普遍用途 
如下所概述，本产品已在各种道路或非道路车辆中进行了实验测试且已经证明当在每10加仑的超低硫或低硫柴油中加入2-3盎司该产品时，实现了磨损减小、里程数增加和排放降低。 
测试程序 
对于超低硫和低硫柴油燃料测试磨损的最新方法为高频往复实验机(HFRR)。ASTM-D 975。燃料进行磨损测试并且必须表现出不大于520微米的磨痕。 
测试结果 
尽管所有经测试的柴油燃料都超过了容许的磨损多达20-30微米，但将本发明的添加物加入到超低硫柴油(每10加仑柴油燃料2.0盎司)使磨痕 降低了容许疤痕尺寸的约28％或者约375微米。 
这种实验测试证明了本发明能够显著降低当前柴油机械装置所承受的磨损。随着就超低硫柴油所开发的进一步的测试ASTM标准，将对本发明进行进一步的实验测试。 
虽然这里仅阐述了本发明的一些优选特征，但是很多修改、变化和替换对本领域技术人员是已知的。因此，应理解的是所附权利要求意欲覆盖所有落入本发明实质精神内的修改和变化。 

Claims (24)

1.一种用于改进润滑的通用合成柴油燃料添加剂，其包含：
α-烯烃；
低气味芳烃溶剂，所述低气味芳烃溶剂的芳烃百分数根据EC-A-G04为5-40%；
至少一种选自由加氢异构化高级基础油和HT剧烈加氢裂化基础油组成的基础油组中的基础油；和
十六烷值促进剂、清洁剂、浊点降低剂混合物。
2.权利要求1的通用合成柴油燃料添加剂，其中所述十六烷值促进剂、清洁剂、浊点降低剂混合物还包含：2-乙基己基硝酸酯。
3.权利要求2的通用合成柴油燃料添加剂，其中所述十六烷值促进剂、清洁剂、浊点降低剂混合物还包含：
石脑油；
萘；和
三甲基苯。
4.权利要求1的通用合成柴油燃料添加剂，其还包含：低闪点溶剂油，其具有15-40℃的闪点。
5.权利要求4的通用合成柴油燃料添加剂，其还包含：磺酸钙。
6.权利要求4的通用合成柴油燃料添加剂，其还包含：
溶剂活化染料；
至少一种选自降凝剂和浊点降低剂的抑制剂；
异构体重整油；和
二甲基酮。
7.权利要求5的通用合成柴油燃料添加剂，其还包含：
溶剂活化染料；
至少一种选自降凝剂和浊点降低剂的抑制剂；
异构体重整油；和
二甲基酮。
8.权利要求1的通用合成柴油燃料添加剂，其中，当所述合成柴油燃料添加剂的成分为如下时：所述α-烯烃；所述低气味芳烃溶剂；所述至少一种基础油；所述十六烷值促进剂、清洁剂、浊点降低剂混合物；磺酸钙；低闪点溶剂油；溶剂活化染料；至少一种抑制剂；异构体重整油；和二甲基酮：
所述α-烯烃占5-30重量%；
所述低气味芳烃溶剂占3-27重量%；
所述至少一种基础油占0.5-15重量%；
所述十六烷值促进剂、清洁剂、浊点抑制剂混合物占0.03-0.25重量%；并且其中，
当省去所述合成柴油燃料添加剂中的一种或多种所述成分时，所述重量百分数按比例增加。
9.权利要求4的通用合成柴油燃料添加剂，其中，当所述合成柴油燃料添加剂的成分为如下时：所述α-烯烃；所述低气味芳烃溶剂；所述至少一种基础油；所述十六烷值促进剂、清洁剂、浊点降低剂混合物；磺酸钙；所述低闪点溶剂油；溶剂活化染料；至少一种抑制剂；异构体重整油；和二甲基酮：
所述α-烯烃占5-30重量%；
所述低气味芳烃溶剂占3-27重量%；
所述至少一种基础油占0.5-15重量%；
所述十六烷值促进剂、清洁剂、浊点抑制剂混合物占0.03-0.25重量%；
所述低闪点溶剂油占15-50重量%；并且其中，
当省去所述合成柴油燃料添加剂中的一种或多种所述成分时，所述重量百分数按比例增加。
10.权利要求5的通用合成柴油燃料添加剂，其中，当所述合成柴油燃料添加剂的成分为如下时：所述α-烯烃；所述低气味芳烃溶剂；所述至少一种基础油；所述十六烷值促进剂、清洁剂、浊点降低剂混合物；所述磺酸钙；所述低闪点溶剂油；溶剂活化染料；至少一种抑制剂；异构体重整油；和二甲基酮：
所述α-烯烃占5-30重量%；
所述低气味芳烃溶剂占3-27重量%；
所述至少一种基础油占0.5-15重量%；
所述十六烷值促进剂、清洁剂、浊点降低剂混合物占0.03-0.25重量%；
所述低闪点溶剂油占15-50重量%；
所述磺酸钙占0.05-0.25重量%；并且其中，
当省去所述合成柴油燃料添加剂中的一种或多种所述成分时，所述重量百分数按比例增加。
11.权利要求6的通用合成柴油燃料添加剂，其中，当所述合成柴油燃料添加剂的成分为如下时：所述α-烯烃；所述低气味芳烃溶剂；所述至少一种基础油；所述十六烷值促进剂、清洁剂、浊点降低剂混合物；磺酸钙；所述低闪点溶剂油；溶剂活化染料；至少一种抑制剂；异构体重整油；和二甲基酮：
所述α-烯烃占5-30重量%；
所述低气味芳烃溶剂占3-27重量%；
所述至少一种基础油占0.5-15重量%；
所述十六烷值促进剂、清洁剂、浊点降低剂混合物占0.03-0.25重量%；
所述低闪点溶剂油占15-50重量%；
所述溶剂活化染料占0.002-0.005重量%；
所述至少一种抑制剂占0.50-2重量%；
所述异构体重整油占0.50-5.0重量%；和
所述二甲基酮占10-50重量%；并且其中，
当省去所述合成柴油燃料添加剂中的一种或多种所述成分时，所述重量百分数按比例增加。
12.权利要求7的通用合成柴油燃料添加剂，其中：
所述α-烯烃占5-30重量%；
所述低气味芳烃溶剂占3-27重量%；
所述至少一种基础油占0.5-15重量%；
所述十六烷值促进剂、清洁剂、浊点降低剂混合物占0.03-0.25重量%；
所述磺酸钙占0.05-0.25重量%；
所述低闪点溶剂油占15-50重量%；
所述溶剂活化染料占0.002-0.005重量%；
所述至少一种抑制剂占0.50-2重量%；
所述异构体重整油占0.50-5.0重量%；和
所述二甲基酮占10-50重量%。
13.权利要求2的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；和
将所述2-乙基己基硝酸酯加入到所述第一混合物中。
14.权利要求3的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；
单独掺混所述2-乙基己基硝酸酯；所述石脑油；所述萘；和所述三甲基苯，从而产生第二混合物；以及
将所述第二混合物加入到所述第一混合物中。
15.权利要求4的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；
单独掺混所述十六烷值促进剂、清洁剂、浊点降低剂混合物，从而产生第二混合物；
将所述第二混合物加入到所述第一混合物中；
将所述低闪点溶剂油加入到所述第一和第二混合物中。
16.权利要求5的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；
单独掺混所述十六烷值促进剂、清洁剂、浊点降低剂混合物，从而生成第二混合物；
将所述第二混合物加入到所述第一混合物中；
单独掺混所述磺酸钙和所述低闪点溶剂油，从而产生第三混合物；以及
将所述第三混合物入到所述第一和第二混合物中。
17.权利要求6的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；
单独掺混所述十六烷值促进剂、清洁剂、浊点降低剂混合物，从而产生第二混合物；
将所述第二混合物加入到所述第一混合物中；
将所述低闪点溶剂油加入到所述第一和第二混合物中；和
将所述溶剂活化染料；所述至少一种抑制剂；所述异构体重整油；和所述二甲基酮加入到所述第一和第二混合物、和所述低闪点溶剂油的混合物中。
18.权利要求7的通用合成柴油燃料添加剂，其通过包括以下步骤的方法制得：
将所述α-烯烃、所述低气味芳烃溶剂和所述至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；
单独掺混所述十六烷值促进剂、清洁剂、浊点降低剂混合物，从而产生第二混合物；
将所述第二混合物加入到所述第一混合物中；
单独掺混所述磺酸钙和所述低闪点溶剂油，从而产生第三混合物；
将所述第三混合物入到所述第一和第二混合物中；和
将所述溶剂活化染料；所述至少一种抑制剂；所述异构体重整油；和所述二甲基酮加入到所述第一、第二和第三混合物中。
19.一种生产通用合成柴油燃料添加剂的方法，其包括：
将α-烯烃、低气味芳烃溶剂和至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；以及
将2-乙基己基硝酸酯加入到所述第一混合物中。
20.权利要求19的方法，其还包括：
将α-烯烃、低气味芳烃溶剂和至少一种基础油掺混直到混合均匀而没有出现任何分离，从而产生第一混合物；以及
单独掺混2-乙基己基硝酸酯；石脑油；萘；和三甲基苯，从而产生第二混合物；以及
将所述第二混合物加入到所述第一混合物中。
21.权利要求20的方法，其还包括：
将低闪点溶剂油加入到所述第一和第二混合物中。
22.权利要求20的方法，其还包括：
单独掺混磺酸钙和低闪点溶剂油，从而产生第三混合物；以及
将所述第三混合物入到所述第一和第二混合物中。
23.权利要求21的方法，其还包括：
将溶剂活化染料；至少一种选自降凝剂和浊点降低剂的抑制剂；异构体重整油；和二甲基酮添加到所述第一和第二混合物、和所述低闪点溶剂油的混合物中。
24.权利要求22的方法，其还包括：
将溶剂活化染料；至少一种选自降凝剂和浊点降低剂的抑制剂；异构体重整油；和二甲基酮添加到所述第一、第二和第三混合物中。
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