CN111349480A - 烃船用燃料油 - Google Patents

烃船用燃料油 Download PDF

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Publication number
CN111349480A
CN111349480A CN201911247079.7A CN201911247079A CN111349480A CN 111349480 A CN111349480 A CN 111349480A CN 201911247079 A CN201911247079 A CN 201911247079A CN 111349480 A CN111349480 A CN 111349480A
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fuel oil
bunker
bunker fuel
iso
mass
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CN201911247079.7A
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CN111349480B (zh
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R·雷
P·克尔比
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Infineum International Ltd
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Infineum International Ltd
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Abstract

一种液态烃船用燃料油，其包含船用馏出燃料或重质燃料油或其掺合物，其含有一种添加剂组合，所述添加剂组合包含：(A)聚烯基取代的羧酸或酐，和(B)金属烃基取代的羟基苯甲酸盐和/或磺酸盐清净剂，其中(A)与(B)的质量:质量比在20:1至1:20的范围内且所述添加剂组合的处理率在5至10000质量ppm的范围内。

Description

烃船用燃料油
发明领域
本发明涉及添加剂在液态烃船用燃料油中用于抑制沥青质附聚和/或絮凝和用于分散沥青质和/或控制在与油接触的表面上的沉积物的用途。
背景技术
沥青质包括大量结构，如具有杂原子的高分子量稠合芳族化合物；它们是主要由碳和氢构成但也含有次要组分如硫、氧、氮和各种重金属的杂环不饱和大分子。它们以显著量存在于船用燃料油中并会在油的运输、储存和使用过程中沉淀析出和沉积以带来不良后果。
业内描述了为解决这一问题而借助添加剂的许多处理。例如，US-A-2017/0306215(“’215”)描述了通过在烃中加入有效量的聚酯沥青质分散剂来抑制烃中的沥青质沉淀和/或沉积，所述聚酯沥青质分散剂可通过使每烷基(烯基)的琥珀酸基团平均数小于2.0的烷基(烯基)取代琥珀酸酐与至少一种多元醇反应获得。
发明内容
概述
本发明以与‘215不同的方式解决上述沥青质问题。其使用例如未反应的琥珀酸酐并与金属清净剂组合，在本说明书的实施例部分中证实其效力。
在第一个方面中，本发明提供一种液态烃船用燃料油，其包含船用馏出物燃料或重质燃料油或其掺合物，所述燃料油含有添加剂组合，其包含：
(A)聚烯基取代的羧酸或酐；和
(B)金属清净剂体系，其包含烃基取代的羟基苯甲酸金属盐、或烃基取代的磺酸金属盐或这两种盐的混合物或其配合物；
其中(A)与(B)的质量:质量比在20:1至1:20，如10:1至1:10，优选3:1至1:3的范围内，且所述添加剂组合的处理率在5、10、100或500至1000、5000或10000，优选100至5,000，如500至1,000质量ppm的范围内。
液态烃船用燃料油可根据(或可符合)ISO 8217:2017、ISO 8217:2012、ISO 8217:2010和ISO 8217:2005的至少一种用于石油产品的船用燃料规格定义；可具有不大于0.5质量％硫原子的硫含量；可完全(全部)或一定程度(部分)由原油借助分馏制成；可使得添加剂(A)和(B)用作清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂和/或助燃剂和/或其它添加剂的一种或多种或与其一起使用；和/或它们的任何组合。
在第二个方面中，本发明提供如上文定义的添加剂组合用于在上文定义的液态烃船用燃料油中抑制沥青质附聚、和/或絮凝、和/或分散沥青质和/或控制沉积到表面上的用途。
在第三个方面中，本发明提供一种在液态烃船用燃料油中抑制沥青质附聚和/或絮凝、和/或分散沥青质和/或控制沉积到表面上的方法，其包括向油中加入有效量的上文定义的添加剂组合。
定义
为了举例说明而非限制，提供下列定义。
“烷基”是指不含双键或三键并排列在支化链或直链中的一价烃基。
“亚烷基”是指不含双键或三键并排列在支化链或直链中的二价烃基。
“烯基”是指含有一个或多个双键并排列在支化链或直链中的一价烃基。
“PIB”是指聚异丁烯并包括正常或“常规”聚异丁烯和高反应性聚异丁烯(HRPIB)。
提到一基团是特定聚合物(例如聚丙烯、聚(乙烯-共聚-丙烯)或PIB)包括主要含有各自的单体以及可忽略不计的量的沿聚合物链的其它取代和/或间隔(interruption)的聚合物。换言之，提到一基团是聚丙烯基团不要求该基团由100％丙烯单体构成而没有任何连接基、取代、杂质或其它取代基(例如亚烷基或亚烯基取代基)。这样的杂质或其它取代基可以相对次要量存在，只要它们与含有100％纯度的各自聚合物取代基(substituent)的相同添加剂相比不影响添加剂的工业性能。
“烃基”是指含有碳和氢原子并经由碳原子键合到该分子的其余部分上的基团或原子团(radical)。其可含有杂原子，即非碳和氢的原子，只要它们不改变该基团的基本烃性质和特征。
如果使用下列词语和措辞，其也具有下文给出的含义：
“活性成分”或“(a.i.)”是指不是稀释剂或溶剂的添加剂材料；
“包含”或任何同源词指定所述要素、步骤或整数或组分的存在，但不排除存在或添加一个或多个其它要素、步骤、整数、组分或其群组；措辞“由...构成”或“基本由...构成”或同源词可能涵盖在“包含”或同源词内，其中“基本由...构成”允许包括不会实质影响其适用的组合物的特征的物质；
“主要量”是指组合物的50质量％或更多，优选60质量％或更多，更优选70质量％或更多，再更优选80质量％或更多；
“次要量”是指组合物的少于50质量％，优选少于40质量％，更优选少于30质量％，再更优选少于20质量％；
“TBN”是指通过ASTM D2896测得的总碱值。
此外，在本说明书中，如果使用：
“钙含量”通过ASTM 4951测得；
“磷含量”通过ASTM D5185测得；
“硫酸盐灰分含量”通过ASTM D874测得；
“硫含量”通过ASTM D2622测得；
“KV100”是指通过ASTM D445测得的在100℃下的运动粘度。
还要理解的是，所用各种组分(基本的以及最佳的和常规的)可能在配制、储存或使用条件下反应，本发明也提供由于任何这样的反应可获得或已获得的产物。
此外，要理解的是，本文列出的量、范围和比率的任何上限和下限可以独立地组合。
具体实施方式
详述
聚烯基取代的羧酸或酐(A)
添加剂组分(A)可以是单或多羧酸，优选二羧酸。聚烯基优选具有8至400，如12至100个碳原子。
(A)内的示例性酐可由下列通式描绘：
Figure BDA0002308000820000041
其中R1代表C8至C100支化或线性聚烯基。
聚烯基结构部分可具有200至10000，优选350至2000，优选500至1000的数均分子量。
用于形成本发明中所用的酐以生成聚烯基结构部分的合适的烃或聚合物包括均聚物、互聚物或较低分子量烃。一类这样的聚合物包括乙烯和/或至少一种具有式H2C＝CHR1的C3至C28α-烯烃的聚合物，其中R1是包含1至26个碳原子的直链或支化链烷基，且其中该聚合物含有碳-碳不饱和，优选高度末端亚乙烯基不饱和。此类聚合物优选包括乙烯和至少一种上式的α-烯烃的互聚物，其中R1是具有1至18，更优选1至8，再更优选1至2个碳原子的烷基。因此，可用的α-烯烃单体和共聚单体包括例如丙烯、丁烯-1、己烯-1、辛烯-1、4-甲基戊烯-1、癸烯-1、十二烯-1、十三烯-1、十四烯-1、十五烯-1、十六烯-1、十七烯-1、十八烯-1、十九烯-1及其混合物(例如丙烯和丁烯-1的混合物)。此类聚合物的实例是丙烯均聚物、丁烯-1均聚物、乙烯-丙烯共聚物、乙烯-丁烯-1共聚物和丙烯-丁烯共聚物，其中该聚合物含有至少一些末端和/或内部不饱和。优选聚合物是乙烯和丙烯以及乙烯和丁烯-1的不饱和共聚物。该互聚物可含有次要量，例如0.5至5摩尔％的C4至C18非共轭二烯烃共聚单体。但是，该聚合物优选仅包含α-烯烃均聚物、α-烯烃共聚单体的互聚物和乙烯与α-烯烃共聚单体的互聚物。所用聚合物的摩尔乙烯含量优选为0至80，更优选0至60％。当使用丙烯和/或丁烯-1作为与乙烯的共聚单体时，此类共聚物的乙烯含量最优选为15至50％，尽管可存在更高或更低的乙烯含量。
这些聚合物可通过使α-烯烃单体、或α-烯烃单体的混合物、或包含乙烯和至少一种C3至C28α-烯烃单体的混合物在包含至少一种茂金属(例如环戊二烯基-过渡金属化合物)和铝氧烷化合物的催化剂体系存在下聚合制备。使用这种方法，可以提供其中95％或更多的聚合物链具有末端亚乙烯基型不饱和的聚合物。表现出末端亚乙烯基不饱和的聚合物链的百分比可通过FTIR能谱分析、滴定或C13 NMR测定。后者类型的互聚物可通过式POLY-C(R1)＝CH2表征，其中R1是C1至C26，优选C1至C18，更优选C1至C8，最优选C1至C2烷基(例如甲基或乙基)，且其中POLY代表聚合物链。R1烷基的链长随选择用于聚合的共聚单体而变。次要量的聚合物链可含有末端乙烯基(ethenyl)，即乙烯基(vinyl)不饱和，即POLY-CH＝CH2，且一部分聚合物可含有内部单不饱和，例如POLY-CH＝CH(R1)，其中R1如上文定义。这些末端不饱和互聚物可通过已知的茂金属化学制备并且也可如美国专利Nos.5,498,809；5,663,130；5,705,577；5,814,715；6,022,929和6,030,930中所述制备。
另一类可用的聚合物是通过异丁烯和苯乙烯的阳离子聚合制成的聚合物。这一类型中的常见聚合物包括通过具有35至75质量％的丁烯含量和30至60质量％的异丁烯含量的C4炼油厂料流在路易斯酸催化剂，如三氯化铝或三氟化硼存在下的聚合获得的聚异丁烯。用于制造聚正丁烯的单体的优选来源是石油进料流，如残液II。在本领域中，例如在美国专利No.4,952,739中，公开了这些原料。聚异丁烯是最优选的骨架，因为其容易由丁烯料流通过阳离子聚合(例如使用AlCl3或BF3催化剂)获得。此类聚异丁烯通常含有沿链布置的每聚合物链一个烯属双键的量的残留不饱和。一个优选实施方案利用由纯异丁烯料流或残液I料流制成的聚异丁烯制备含末端亚乙烯基烯烃的反应性异丁烯聚合物。优选地，被称为高反应性聚异丁烯(HR-PIB)的这些聚合物具有至少65％，例如70％，更优选至少80％，最优选至少85％的末端亚乙烯基含量。例如在美国专利No.4,152,499中描述了此类聚合物的制备。HR-PIB是已知的且HR-PIB可以商品名GlissopalTM(来自BASF)和UltravisTM(来自BP-Amoco)购得。
可用的聚异丁烯聚合物通常基于400至3000的烃链。制造聚异丁烯的方法是已知的。聚异丁烯可如下所述通过卤化(例如氯化)、热“烯”反应或通过使用催化剂(例如过氧化物)的自由基接枝官能化。
烃或聚合物骨架可以使用上文提到的三种方法的任一种或其任何顺序的组合，选择性地在该聚合物或烃链上的碳-碳不饱和位点处或沿链无规地用产生羧酸酐的结构部分(moieties)官能化。
用于使聚合烃与不饱和羧酸、酐反应的方法和由这些化合物制备衍生物的方法公开在美国专利Nos.3,087,936；3,172,892；3,215,707；3,231,587；3,272,746；3,275,554；3,381,022；3,442,808；3,565,804；3,912,764；4,110,349；4,234,435；5,777,025；5,891,953；以及EP 0 382 450B1；CA-1,335,895和GB-A-1,440,219中。该聚合物或烃可通过使用卤素辅助的官能化(例如氯化)法或热“烯”反应在导致官能结构部分或试剂(即酸酐)主要在碳-碳不饱和(也称为烯键或烯属不饱和)位点处加成到该聚合物或烃链上的条件下使该聚合物或烃反应而用羧酸酐结构部分来官能化。
可以通过在60至250，优选110至160，例如120至140℃的温度下将氯或溴通过该聚合物0.5至10，优选1至7小时而将不饱和α-烯烃聚合物卤化，例如氯化或溴化至基于聚合物或烃的重量计1至8，优选3至7质量％氯或溴来实现选择性官能化。该卤化聚合物或烃(下文称为骨架)随后与足量的能将所需数量的官能结构部分加成到骨架上的单不饱和反应物(例如单不饱和羧酸反应物)在100至250，通常180至235℃下反应0.5至10，例如3至8小时，以使所得产物含有每摩尔卤化骨架所需摩尔数的单不饱和羧酸反应物。或者，将骨架和单不饱和羧酸反应物混合并在向该热材料中加入氯的同时加热。
尽管氯化通常有助于提高原料烯烃聚合物与单不饱和官能化反应物的反应性，但这对考虑用于本发明的一些聚合物或烃而言不是必要的，特别是具有高端键含量和反应性的那些优选聚合物或烃。因此，优选使骨架和单不饱和官能化反应物(羧酸反应物)在升高的温度下接触以引发初始热“烯”反应。烯反应(Ene reactions)是已知的。
可通过经各种方法沿聚合物链无规连接官能结构部分来将烃或聚合物骨架官能化。例如，该聚合物可以以溶液或固体形式在自由基引发剂存在下用如上所述的单不饱和羧酸反应物接枝。当在溶液中进行时，接枝在100至260，优选120至240℃的高温下进行。自由基引发的接枝优选在含有例如基于初始总油溶液计1至50，优选5至30质量％聚合物的矿物润滑油溶液中实现。
可用的自由基引发剂是过氧化物、氢过氧化物和偶氮化合物，优选是沸点高于100℃并在接枝温度范围内热分解以提供自由基的那些。这些自由基引发剂的代表是偶氮丁腈、2,5-二甲基己-3-烯-2,5-双叔丁基过氧化物和过氧化二枯烯。该引发剂在使用时通常以基于反应混合物溶液重量计的0.005至1重量％的量使用。通常，上述单不饱和羧酸反应物材料和自由基引发剂在1.0:1至30:1，优选3:1至6:1的重量比范围内使用。该接枝优选在惰性气氛中，如在氮气覆盖下进行。所得接枝聚合物的特征在于具有沿聚合物链无规连接的羧酸(或衍生物)结构部分，要理解的是，一些聚合物链保持未接枝。上述自由基接枝可用于本发明中所用的其它聚合物和烃。
用于将骨架官能化的优选单不饱和反应物包含单-和二羧酸材料，即酸或酸衍生材料，包括(i)单不饱和的C4至C10二羧酸，其中(a)羧基是邻位的(即位于相邻碳原子上)和(b)相邻碳原子的至少一个，优选两者都是单不饱和的一部分；(ii)(i)的衍生物，如酐或C1至C5醇衍生的(i)的单酯或二酯；(iii)单不饱和的C3至C10单羧酸，其中碳-碳双键与羧基共轭，即具有结构-C＝C-CO-；和(iv)(iii)的衍生物，如C1至C5醇衍生的(iii)的单酯或二酯。也可使用单不饱和的羧酸材料(i)-(iv)的混合物。在与骨架反应时，单不饱和羧酸反应物的单不饱和变饱和。因此，例如，马来酸酐变成骨架取代的琥珀酸酐，丙烯酸变成骨架取代的丙酸。此类单不饱和羧酸反应物的实例是富马酸、衣康酸、马来酸、马来酸酐、氯马来酸、氯马来酸酐、丙烯酸、甲基丙烯酸、巴豆酸、肉桂酸和前述的低碳烷基(例如C1至C4烷基)酸酯，例如马来酸甲酯、富马酸乙酯和富马酸甲酯。
为了提供所需官能度，单不饱和羧酸反应物，优选马来酸酐，通常以基于聚合物或烃的摩尔计等摩尔量至100，优选5至50质量％过量的量使用。如果需要，可以通过例如汽提(通常在真空下)从最终分散剂产物中除去未反应的过量单不饱和羧酸反应物。
金属清净剂(B)
金属清净剂是基于所谓金属“皂”(即酸性有机化合物的金属盐)的添加剂，有时称为表面活性剂。可用的清净剂包括金属，特别是碱金属或碱土金属，例如钠、钾、锂、钙和镁的油溶性中性和过碱性水杨酸盐和磺酸盐。最常用的金属是钙和镁，两者都可存在于根据本发明的任一方面的船用燃料组合物中使用的清净剂中。可以使用清净剂的组合，无论是过碱性还是中性还是两者。它们通常包含极性头和长疏水尾。可以通过使过量金属碱(如氧化物或氢氧化物)与酸性气体(如二氧化碳)反应而包括大量金属碱，以提供包含中和的金属清净剂作为金属碱(例如碳酸盐)胶束的外层的过碱性金属清净剂。
在本发明中，金属清净剂(B)可以是烃基取代的羟基苯甲酸金属盐，更优选烃基取代的水杨酸盐清净剂。该金属可以是碱金属(例如Li、Na、K)或碱土金属(例如Mg、Ca)。
作为烃基的实例，可以提到烷基和烯基。优选的烃基取代的羟基苯甲酸金属盐是烷基取代的水杨酸钙并具有下示结构：
Figure BDA0002308000820000081
其中R是线性烷基。可以有多于一个R基团连接到苯环上。COO-基团可以在羟基的邻位、间位或对位；邻位是优选的。R基团可以在羟基的邻位、间位或对位。
水杨酸通常通过酚盐的羧化、通过Kolbe-Schmitt法制备，在这种情况下通常与未羧化的酚混合获得(通常在稀释剂中)。水杨酸可以是未硫化或硫化的，并且可以化学改性和/或含有附加取代基。硫化烷基水杨酸的方法是本领域技术人员公知的，并描述在例如US2007/0027057中。
烷基可含有8至100，有利地8至24，如14至20个碳原子。
本发明的磺酸盐可由磺酸制备，所述磺酸通常通过烷基取代的芳烃(如由石油分馏或通过芳烃的烷基化获得的那些)的磺化获得。实例包括通过将苯、甲苯、二甲苯、萘、联苯或它们的卤素衍生物，如氯苯、氯甲苯和氯萘烷基化而得的那些。可在催化剂存在下用具有3至多于70个碳原子的烷基化剂进行烷基化。烷芳基磺酸盐通常含有每烷基取代的芳族结构部分9至80个或更多碳原子，优选16至60个碳原子。该油溶性磺酸盐或烷芳基磺酸可用金属的氧化物、氢氧化物、醇盐、碳酸盐、羧酸盐、硫化物、氢硫化物、硝酸盐、硼酸盐和醚中和。考虑最终产物的所需TBN来选择金属化合物的量，但通常为化学计算所需量的100至220质量％(优选至少125质量％)。
术语“过碱性(overbased)”常用于描述金属结构部分的当量数与酸结构部分的当量数的比率大于1的金属清净剂。术语“低碱性(low-based)”用于描述金属结构部分与酸结构部分的当量比大于1且最多大约2的金属清净剂。
“表面活性剂的过碱性钙盐”是指其中油不溶性金属盐的金属阳离子基本是钙阳离子的过碱性清净剂。在该油不溶性金属盐中可存在少量的其它阳离子，但该油不溶性金属盐中通常至少80，更通常至少90，例如至少95摩尔％的阳离子是钙离子。钙以外的阳离子可例如衍生自在过碱性清净剂的制造中使用其中阳离子是钙以外的金属的表面活性剂盐。表面活性剂的金属盐优选也是钙。
碳酸化的过碱性金属清净剂通常包含非晶纳米粒子。另外，本领域公开了包含结晶方解石和球霰石(vaterite)形式的碳酸盐的纳米微粒材料。
清净剂的碱度可表示为总碱值(TBN)，有时称为碱值(BN)。总碱值是中和过碱性材料的所有碱度所需的酸的量。可以使用ASTM标准D2896或等效程序测量TBN。该清净剂可具有低TBN(即小于50的TBN)、中TBN(即50至150的TBN)或高TBN(即大于150，如150-500的TBN)。碱度也可表示为碱度指数(BI)，其是过碱性清净剂中的总碱与总皂的摩尔比。
添加剂组合
本发明的船用燃料油包含可由(或基本由)添加剂(A)和(B)构成的添加剂组合。相应地，尽管本文中提到的添加剂组合的处理率考虑的是其中的活性成分(A)和(B)对船用燃料油的处理率，但要理解的是，该添加剂组合可与溶剂、稀释剂或其它添加剂(如清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂或助燃剂)结合或同时引入船用燃料油中。其它添加剂如上列那些可以附加地或替代性地与本发明中提到的添加剂组合分开地(例如在该添加剂组合之前或之后)添加或与船用燃料油掺合。
船用燃料油
本发明的船用燃料油可根据ISO 8217:2017、ISO 8217:2012、ISO 8217:2010和/或ISO 8217:2005的石油产品的船用燃料规格定义。要理解的是，根据本发明的船用燃料可附加地或替代性地满足其它ISO 8217版本、地区规格和/或供应商/运营商规格。
该油可具有不大于0.5，例如小于0.5、不大于0.4、小于0.4、不大于0.3、小于0.3、不大于0.2、小于0.2、不大于0.1或小于0.1质量％硫原子的硫含量。在一些优选实施方案中，船用燃料油的硫含量可小于0.5或甚至小于0.1质量％硫原子。
例如，所有或一部分本发明的船用燃料油可由原油借助分馏制成。
在本发明的船用燃料油中，添加剂(A)和(B)可用作清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂或助燃剂的一种或多种或与其一起使用。换言之，由(A)和(B)构成的添加剂组合可与一种或多种其它添加剂(如清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂或助燃剂)一起使用。
在(B)中，所述或各清净剂可具有在下限为0、50、100或150且上限为300、350、400、450或500的范围内的TBN。
清净剂(B)可以是中性或过碱性的，优选过碱性的。(A)与(B)的质量:质量比可在1:1至1:6，如1:1至1:3的范围内。
本发明可包括船用燃料油的储存和/或调合。
实施例
下列非限制性实施例例示本发明。
船用燃料
使用下列燃料
燃料R根据用于船用残余燃料的公开ISO 8217 2017FUEL STANDARD表征并如该标准中被识别为RMG 380且具有2.4％的硫含量的船用残余燃料
燃料R/D根据用于船用残余燃料的公开ISO 8217 2017FUEL STANDARD表征并如该标准中被识别为RMG 380且具有1.5％的硫含量的船用残余燃料和根据用于船用馏出物燃料的公开ISO 8217 2017FUEL STANDARD表征的船用馏出物燃料的掺合物，所得硫含量为0.48％。
使用下列添加剂组分。
组分(A)
80％具有950的数均分子量的衍生自聚异丁烯的聚异丁烯琥珀酸酐(“PIBSA”)和20％SNISO形式的稀释剂，I类油组分(B)
B1具有225的TBN的过碱性水杨酸钙清净剂
B2具有302的TBN的过碱性磺酸钙清净剂
测试
根据名称为“Standard Test Method for Measuring n-Heptane Induced PhaseSeparation of Asphaltene-Containing Heavy Fuel Oils as Separability Number byan Optical Scanning Device”的ASTM D7061-17测试含有或不含添加剂组分的上述燃料样品的沥青质分散力。可分离性值结果可被称为“RSN”。
结果概括在下表中。
表1
Figure BDA0002308000820000121
所得可分离性值显示在“燃料”列中，其中较低值表示优异的性能。看出本发明的实施例1-7实现比对照物和比对比例1和2好的性能。
(Mg)是指使用镁盐。
*处理率仅涉及R部分。
与实施例3、5和7有关的进一步实施例概括在下表2中，其中使用不同的船用残余燃料。结果证实，对于本发明的实施例，性能始终好于对照例。
表2
Figure BDA0002308000820000131

Claims (17)

1.一种液态烃船用燃料油，其包含船用馏出物燃料或重质燃料油或其掺合物，所述燃料油包含一种添加剂组合，其如下构成：
(A)聚烯基取代的羧酸或酐；和
(B)金属清净剂体系，其包含烃基取代的羟基苯甲酸金属盐或烃基取代的磺酸金属盐或这两种盐的混合物或其配合物；
其中(A)与(B)的质量:质量比在20:1至1:20，如10:1至1:10，优选3:1至1:3的范围内，且所述添加剂组合的处理率在5、10、100或500至1000、5000或10000，优选100至5,000，如500至1,000质量ppm的范围内；
并且其中：
i.所述燃料油根据ISO 8217:2017、ISO 8217:2012、ISO 8217:2010和/或ISO 8217:2005的至少一种用于石油产品的船用燃料规格定义；
ii.所述燃料油具有不大于0.5质量％硫原子的硫含量；
iii.所有或一部分燃料油由原油借助分馏制成；
iv.添加剂(A)和(B)用作清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂和/或助燃剂和/或其它添加剂的一种或多种，或与清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂和/或助燃剂和/或其它添加剂的一种或多种一起使用；或
v.i.至iv.的任何组合。
2.权利要求1的船用燃料油，其根据ISO 8217:2017、ISO 8217:2012、ISO 8217:2010和/或ISO 8217:2005的用于石油产品的船用燃料规格定义。
3.权利要求1或权利要求2的船用燃料油，其具有不大于0.5、小于0.5、不大于0.4、小于0.4、不大于0.3、小于0.3、不大于0.2、小于0.2、不大于0.1或小于0.1质量％硫原子的硫含量。
4.权利要求1至3任一项的船用燃料油，其全部或部分由原油借助分馏制成。
5.权利要求1至4任一项的船用燃料油，其中(A)与(B)的质量:质量比在1:1至1:6，如1:1至1:3的范围内。
6.权利要求1至5任一项的船用燃料油，其中在(A)中，所述聚烯基取代基具有8至400，优选12至100，更优选16至64个碳原子。
7.权利要求1至6任一项的船用燃料油，其中在(A)中，所述聚烯基取代基具有350至2000，优选500至1000的数均分子量。
8.权利要求1至7任一项的船用燃料油，其中(A)是琥珀酸酐。
9.权利要求8的船用燃料油，其中(A)是聚异丁烯琥珀酸酐。
10.权利要求1至9任一项的船用燃料油，其中在(B)中，所述金属是钙。
11.权利要求1至10任一项的船用燃料油，其中在(B)中，所述烃基取代的羟基苯甲酸盐是水杨酸盐。
12.权利要求1至11任一项的船用燃料油，其中在(B)中，所述烃基具有8至100，如8至24，优选14至20个碳原子。
13.权利要求1至12任一项的船用燃料油，其中在(B)中，所述清净剂具有在下限为0、50、100或150且上限为300、350、400、450或500的范围内的TBN。
14.权利要求1至13任一项的船用燃料油，其中(B)所述或各清净剂作为过碱性清净剂存在。
15.权利要求1至14任一项的船用燃料油，其中添加剂(A)和(B)用作清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂和/或助燃剂和/或其它添加剂的一种或多种，或与清净剂、分散剂、稳定剂、破乳剂、防乳剂、腐蚀抑制剂、低温流动改进剂如倾点下降剂和CFPP改性剂、粘度改进剂、润滑改进剂和/或助燃剂和/或其它添加剂的一种或多种一起使用。
16.如权利要求1和5至15任一项中所述的添加剂(A)和(B)的组合用于在权利要求1至4任一项中所述的液态烃船用燃料油中抑制沥青质附聚、和/或絮凝、和/或分散沥青质和/或控制沉积到表面上的用途。
17.一种在液态烃船用燃料油中抑制沥青质附聚和/或絮凝、和/或分散沥青质和/或控制沉积到表面上的方法，其包括向油中加入有效量的权利要求1和5至15任一项中所述的添加剂(A)和(B)的组合。
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