CN1138848C - 异构烷烃润滑油基础油组合物 - Google Patents

异构烷烃润滑油基础油组合物 Download PDF

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CN1138848C
CN1138848C CNB988112280A CN98811228A CN1138848C CN 1138848 C CN1138848 C CN 1138848C CN B988112280 A CNB988112280 A CN B988112280A CN 98811228 A CN98811228 A CN 98811228A CN 1138848 C CN1138848 C CN 1138848C
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T��R��С����˹
T·R·小福布斯
Z·江
��������ķ������
R·D·帕特瑞治
ά
S·E·施拉姆
J·C·特瑞维拉
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Abstract

一种含有烷烃组分的液体烃类组合物，其中对所述的液体烃类组合物作为整体测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：(a)BI-0.5(CH2＞4)＞15；以及(b)BI+0.85(CH2＞4)＜45。

Description

异构烷烃润滑油基础油组合物
本申请根据35U.S.C.§119要求美国临时申请No.60/062824的优先权。
已研制出具有独特组成特性的高性能的润滑油基础油，并已证明它们具有优良的低温性能。
优质高性能的润滑油基础油通常在宽的温度范围具有有效的粘度，具有高的粘度指数，以及证明其润滑性、热稳定性和氧化稳定性以及倾点等于或优于传统的矿物油。相对于矿物油为基础的配方，这样的有利的流变性能和其他性能提高了它们在润滑油配方中的性能，这些性能包括更宽操作温度范围。但是，这样的优质润滑油基础油比传统的矿物油润滑油有更高的生产费用。
许多研究人员已研究出将相对低价值的烃类原料例如天然气转化成更高价值的产品例如燃料和润滑油的多条途径。此外，已进行了许多研究工作，这些研究工作通过加氢异构法和脱蜡法将含有大量直链烷烃组分的含蜡烃类原料催化改质成更有用的产品，加氢异构化法和脱蜡法分别将原料中的直链烷烃含蜡组分异构化和裂化。
由合成气-一种氢和一氧化碳的混合物生产烃类燃料和润滑油的方法已经知道多时，其中费-托合成(FT)法可能是最熟悉的。在Kirk-Othmer，化工百科全书，第三版，John Wiley & Sons，纽约，1980，第11卷，第473-478页中描述了费-托合成法的发展及其一些更值得注意的特性。
在费-托合成法中，通常通过甲烷的部分氧化制得的合成气在升温和升压下在催化剂上通过，生成包括烃类、醇类、脂肪酸类和其他含氧化合物在内的许多一氧化碳的还原产物。在有利的情况下，含氧化合物材料可为全部所需液体产物的1％以下。烃类产物在性质上是高度烷属的，通常包括烃类气体、轻质烯烃、汽油、轻质燃料油和重质燃料油以及含蜡瓦斯油。因为对于用作燃料或润滑油来说，产物中的较高沸点的馏分通常含蜡太多，所以在它们使用以前，或者就这样使用以前，或者加到通用的产品贮罐以前，通常需要进一步加工或改质。有利的是，由于原料相当纯：即氢和一氧化碳，归根到底是甲烷或天然气相当纯，所以费-托合成产物含有很少的(如果有的话)典型石油杂质，例如芳族化合物、环烷烃化合物、含硫化合物和含氮化合物。
US4500417公开了费托合成产物中的高沸点馏分通过与高硅的大孔沸石和加氢组分接触进行的转化，生产馏分油馏分和高粘度指数(VI)和低倾点的润滑油馏分。催化剂包括丫型沸石、β型沸石、丝光沸石、ZSM-3、ZSM-4、ZSM-18和ZSM-20。
US4906350公开了一种制备具有高VI和低倾点的润滑油基础油的方法，该法包括至少一部分含蜡的矿物油馏分的加氢裂化油在选自ZSM-5、ZSM-11、ZSM-23、ZSM-35、ZSM-12、ZSM-38、ZSM-48、菱钾沸石、镁碱沸石、β沸石、θ沸石、α沸石及其混合物的沸石催化剂上催化脱蜡。
US4943672公开了一种费托合成蜡加氢异构化生产具有高VI和低倾点的润滑油的方法，该法包括首先在相对苛刻的条件下加氢处理费托合成蜡，随后在氢存在下将加氢处理的蜡在特殊氟化的第VIII族金属/氧化铝催化剂上加氢异构化。
US5059299公开了一种通过在第VI-VII族金属/卤化的难熔金属氧化物载体催化剂上异构化随后熔剂脱蜡使矿物油得到的含油蜡以及蜡异构化制成高VI的很低倾点的润滑油基础油的方法。
US5135638和5246566公开了通过含蜡石油原料在有一定孔径和至少一种第VIII族金属的分子筛上异构化来生产具有极好粘度、VI和低倾点的润滑油的蜡异构化方法。催化剂包括SAPO-11、SAPO-31、SAPO-41、ZSM-22、ZSM-23和ZSM-35。
US5282958公开了一种使用具有特定孔形状和含有至少一种第VIII族金属的催化剂使含有10个或10个以上碳原子的直链烷烃和稍分支烷烃的烃类进料脱蜡来生产脱蜡润滑油的方法。原料在氢存在下与催化剂接触；例证性的催化剂包括SSZ-32、ZSM-22和ZSM-23。
US5306860公开了一种费托合成生产的烷烃在包括丫型沸石催化剂在内的一系列催化剂上加氢异构化生产高VI、低倾点润滑油的方法。
US 5362378公开了费托合成重质产物用低α活性的铂/硼-β沸石催化剂转化生产极高VI的润滑油，然后用传统的溶剂脱蜡法或通过提高加氢异构化步骤的苛刻度使生成的润滑油脱蜡。
EP 0776959 A2公开了一种由费托合成蜡进料制备VI至少为150的润滑油基础油的方法，该法包括首先在氢存在下在适合的催化剂上加氢异构化，然后使390℃+中间馏分油溶剂脱蜡或催化脱蜡。
但是，上述参考文献中没有一个公开或提出具有任何特定的分支性质组合的特定和有限范围组合物的液体烃类的制备，它产生一些高度希望的润滑性质，包括意想不到的高粘度指数和低倾点的组合。事实上，上述参考文献中甚至没有一个公开或提出测量正如下面讨论的分支指数(BI)或分支接近度。
US 4827064公开了聚α烯烃的高VI合成润滑油组合物，其中测量了“分支比”，即CH3/CH2。
因此上述美国专利的全部公开内容作为参考并入。
本发明的第一个目的是生产这样一种独特的液体烃类组合物，它可适用作具有有效低温粘度性质的润滑油基础油。
本发明的另一目的是通过费托合成、加氢异构化和催化脱蜡步骤的组合使低价值的天然气转化成优质润滑油基础油，为低价值的天然气提供一条出路。
本发明的一个实施方案涉及这样一种含有烷烃组分的液体烃类组合物，其中对液体烃类组合物作为整个测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
本发明的另一实施方案涉及这样一种含有烷烃组分的液体烃类组分的润滑油组合物，其中，对润滑油基础油组合物作为整体测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
在另一实施方案中，本发明涉及这样一种含有烷烃组分的液体烃类组合物的润滑油组合物，其中，对液体烃类组合物作为整个测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45；及任选有效数量的润滑油添加剂，例如但不限于抗氧化剂、抗磨添加剂、极压添加剂、摩擦改进剂、粘度指数改进剂、降凝剂、清净剂、分散剂、腐蚀抑制剂、金属钝化剂、密封相容性添加剂、抗乳化剂、抗泡沫剂及其混合物。
结合附图，从以下的详细描述中会更好地理解本发明上述的和其他的目的、特性和优点，所有这些只是为了说明本发明，而不是对本发明的限制。
图1为本发明的液体烃类组合物与典型加氢处理的润滑油基础油的低温粘度性质比较图。
图2为数学上说明如式(a)和(b)中所示的BI和CH2＞4的结构限制图，它定义了这里公开的本发明组合物的限制。
图3为包括本发明的烃类液体在内的各种烃类液体的动态粘度(DV@-40℃)(用CCS法ASTM D5392测量的)和动力粘度(KV@100℃)的比较图。
从这里给出的详细描述中本发明的另一些应用范围将变得很清楚。但是，应当理解，这些详细描述和具体的实施例虽然可说明本发明的优选实施方案，但它们仅作为说明被给出，因为对于熟悉本专业的技术人员来说，从这一详细描述中，在本发明的精神实质和范围内的各种改变和改进是显而易见的。
本发明的一个实施方案涉及这样一种含烷烃组分的液体烃类组合物，其中，对液体烃类组合物作为整体测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
本发明的烃类流体的BI优选大于或等于25.4，而分支接近度(CH2＞4)优选小于或等于22.5，虽然打算将任何一种满足式(a)和(b)限制的组合物包括在本发明的范围内。
根据本发明，用核磁共振(NMR)分析法进行液体烃类的分支特性的测量，以下将作更详细地描述。
本发明的液体烃类组合物可有很低浓度的由天然矿物油精炼得到的润滑油基础油中找到的典型杂质，它与用于生产液体烃类的原料性质有关。通常，本发明的液体烃类组合物含有＜0.1％(重量)芳烃、＜20ppmW含氮化合物、＜20ppmW含硫化合物以及低浓度的环烷烃。预计这些杂质的含量可能很低，或者在本发明的液体烃类中完全不存在。因此，当由费托合成蜡生产时，在本发明的烃类组合物中，含硫化合物和含氮化合物的浓度优选都＜10ppm、更优选都＜1ppm。
含硫化合物和含氮化合物的低浓度主要是由于原料的性质。由相当纯的合成气混合物(它们在气相中有很少的(如果有的话)含氮化合物或含硫化合物)生成的费托合成蜡的应用得到有很低典型杂质含量的烃类流体。相反，天然存在的矿物油有相当浓度的有机含硫化合物和含氮化合物，它们难以或不可能用商业的物理分离技术例如蒸馏除去。
本发明的液体烃类中有低含量芳烃和环烷烃的原因有两方面：首先，费托合成生产的原料固有地含有低含量的含环分子，因为该转化法主要生成和几乎全部生成线型的碳链；其次，仔细的选择用于生成本发明材料的方法的烃类转化催化剂和条件大大减少在加氢异构化和催化脱蜡过程中芳烃和环烷烃的生成量。
虽然为了在产物流体中得到很低的杂质含量，由费托合成生产的材料来生产本发明的液体烃类是优选的，但是其他的含蜡烃类材料，例如传统的含蜡润滑油提余油、含油蜡、脱油的含油蜡、蜡下油和润滑油馏分油加氢裂化油也可用来生产本发明的烃类组合物。
平均来说，本发明的液体烃类组合物为每100个碳原子有小于10个己基或更长的分支的烷烃。同样，本发明的液体烃类组合物为每100个碳原子平均有16个以上甲基分支的烷烃。用于生产本发明液体烃类的加氢脱蜡步骤使含蜡原料中的长链烷烃大量异构化，得到如式(a)和(b)中描述的有许多分支的烷烃组分。
本发明的烃类流体用作润滑油基础油，即用作配方润滑油的组分，也就是说与其他润滑油基础油，例如矿物油、聚α烯烃、酯类、聚链烯烃、烷基化的芳烃、加氢裂化油和溶剂精制基础油组合。
在另一实施方案中，本发明涉及这样一种含有烷烃组分的润滑油基础油组合物，其中对润滑油基础油组合物作为整个测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
本发明的润滑油基础油主要含有正常沸点为370℃+的异构烷烃组分，其独特性在于，它们意想不到地有高粘度指数和极低倾点的极好组合。在本专业中通常已知这两个特性以正比例相关的，也就是说，降低烃类流体的倾点会使粘度指数下降，所以在同一流体中得到极低倾点和相对高VI是十分不平常的。例如，传统的矿物油基础油，例如这里的对比例3-5当推进到低倾点范围时，就有相对低的VI(表1)。
但是，本发明的基础油的特征为极低的倾点(PP)，即小于或等于-18℃、优选小于或等于-30℃、更优选小于或等于-40℃；100℃的动力粘度(KV)为2至大于13厘沱、优选4-8厘沱；高的粘度指数(VI)，即为130-165、优选140-165、更优选150-165；以及有上述式(a)和(b)中所示的BI和CH2＞4值。
具体地说，本发明的优选产品为有以下性质的润滑油基础油：VI和倾点的组合为130VI/-66℃至165VI/-27℃、更优选144VI/-40℃至165VI/-27℃。
适用于这里公开的含蜡原料转化成本发明的烃类组分的烃类转化催化剂为沸石催化剂，例如US 4906350中公开的ZSM-5、ZSM-11、ZSM-23、ZSM-35、ZSM-12、ZSM-38、ZSM-48、菱钾沸石、镁碱沸石、β沸石、θ沸石、α沸石。这些催化剂与第VIII族金属，特别是钯或铂组合使用。可用传统的技术例如离子交换将第VIII族金属结合到沸石催化剂中。
生产本发明润滑油基础油的方法可为加氢脱蜡法。该加氢脱蜡法可在组合催化剂上或单一催化剂上进行。在500-20000千帕的压力范围下，转化温度可为200-500℃。这一方法在氢存在下操作，氢分压通常为600-6000千帕。氢与烃类进料比(氢循环速率)通常为10-3500标升/升(56-19660标英尺3/桶)，原料的空速通常为0.1-20LHSV、优选0.1-10LHSV。
例如，含蜡原料可在Pt/β沸石和Pt/ZSM-23的组合催化剂上、在氢存在下进行转化。另一方面，生产本发明润滑油基础油的方法可包括在单一催化剂例如Pt/ZSM-35上的加氢异构化和脱蜡。在这两种情况下都可得到本发明独特的产品。
在另一实施方案中，本发明涉及这样一种含有烷烃组分的液体烃类组合物的润滑油组合物，其中对液体烃类组合物作为整个测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45；及任选有效数量的润滑油添加剂，例如抗氧化剂、抗磨添加剂、极压添加剂、摩擦改进剂、粘度指数改进剂、降凝剂、清净剂、分散剂、腐蚀抑制剂、金属钝化剂、密封相容性添加剂、抗乳化剂、抗泡沫剂及其混合物。
在Dieter Klaman著 润滑剂及相关的产品，第9章，第177-217页，Verlag Chemie GmbH(1984)中提供了一篇传统润滑剂添加剂的调查报告，它提出某些适合的抗氧化剂如酚或芳胺类；防锈添加剂如苯并噻唑类；金属钝化剂如乙二胺和咪唑类；VI改进剂如聚异丁烯和聚甲基丙烯酸酯类；降凝剂如长链烷基酚和邻苯二甲酸二烷基芳基酯类。作为分散剂，例如公开了聚亚烷基琥珀酰亚胺类；作为清净剂，公开了这样的化合物，例如磺酸盐类、酚盐类、磺化的酚盐类、磷酸盐类等。还公开了抗磨剂和极压添加剂的应用，它们可包括有机硫化物类、二硫代氨基甲酸金属盐类、氯化的石蜡和有机含磷化合物，例如二硫代磷酸金属盐类；摩擦改进剂，例如长链脂肪酸类、脂肪醇类和脂肪酯类；作为抗泡沫添加剂，聚二甲基硅氧烷类和聚乙二醇醚类和聚乙二醇酯类是已知的；作为密封相容性添加剂，例如芳烃类、醛类、酮类和酯类化合物；作为抗乳化剂，二壬基萘磺酸盐类是已知的；以及作为腐蚀抑制剂，叔胺类、脂肪酸酰胺类、磷酸衍生物和磺酸类是一些例子。熟悉本专业的技术人员会认识到，在本专业中许多其他的这样的添加剂化合物也是已知的，并可用于本发明的基础油。
本发明的润滑油组合物还可含有其他润滑油基础油，例如矿物油、聚α烯烃、酯类、聚链烯烃、烷基化的芳烃、加氢裂化油和溶剂精制的基础油，它们与这里所述的烷烃组分组合。本发明的烷烃组合物可作为润滑油组合物的主要基础油，多种其他传统的润滑油基础油加入其中，或者可在与主要数量的另一润滑油基础油的组合中用作添加物。但是，本发明的液体烃类组合物的浓度至少为全部润滑油基础油组合物的5％(重量)是优选的。
实施例
在以下的实施例中，通过改变加氢异构化和催化脱蜡的反应条件来得到所需的产物，典型的条件范围是但不限于在反应器进口处，200-370℃、400-2000psig、0.50-2.0小时-1LHSV和1900-5000标英尺3/桶氢气。
润滑油基础油的物理性质
实施例1-4
经加氢的费托合成蜡(Paraflint80)在氢存在下、在Pt/β沸石加氢异构化催化剂和Pt/ZSM-23选择性脱蜡催化剂的组合催化剂上进行加氢脱蜡。在不断提高加工条件苛刻度下得到4种不同的烃类流体，它们有表1所示的KV、VI和PP值。实施例4为本发明的一个实施例。
实施例5和6
经加氢和部分异构化的中间馏分油合成蜡提余油(Shell MDS或“SMDS”)在氢存在下、在用于实施例1-4的组合催化剂上进行加氢脱蜡。在不断提高加工条件苛刻度下得到两种不同的烃类流体，它们有表1所示的KV、VI和PP值。实施例6为本发明的一个实施例。
实施例7-9
实施例5和6的Shell MDS原料油在合成的镁碱沸石上、在氢存在下、在不同的条件苛刻度下进行加氢脱蜡，生成三种不同的烃类流体，它们有表1所示的KV、VI和PP值。实施例7-9都是本发明的实施例。
实施例10
用于实施例1-4的含蜡原料油在氢存在下、在Pt/ZSM-48上进行加氢脱蜡，生成有表1所示的KV、VI和PP值的烃类流体。实施例10为本发明的一个实施例。
对比例1、2和6
100℃下KV为3.87厘沱和5.51厘沱的商业制备的聚α烯烃基础油的特征为：倾点＜-65℃，VI分别为130(对比例1)和135(对比例2)。还包括100℃下KV为150厘沱的商业上更高粘度级别的聚α烯烃(对比例6)。
对比例3-5
还评价了几种由加氢裂化原油馏分得到的商业制备的基础油。它们包括：由含油蜡加氢异构化得到的Shell XHVI基础油(倾点-18℃、5.1厘沱KV@100℃、VI147)(对比例3)；Yukong 100N基础油(倾点-15℃、4.0厘沱KV@100℃、VI114)(对比例4)和Cherron RLOP 240N基础油(倾点-15℃、6.9厘沱KV@100℃、VI102)(对比例5)。
各种商业润滑油基础油的典型物理性质与本发明的ULPP(超低倾点)FT异构化油在下表1中进行比较。
                           表1
                       基础油性质说明                 动力粘度          粘度指数         倾点
                 厘沱@100℃                         ℃ParaflintC80蜡(进料)  9.42               -               83实施例1               7.14              177              12实施例2               6.52              171              -3实施例3               5.72              161             -24实施例4*             5.54              145             -63SMDS含蜡抽余油(进料)  5.07               -               39实施例5               5.23              142             -24实施例6*             5.11              130             -66实施例7*             5.33              149             -18实施例8*             5.23              136             -59实施例9*             5.46              144             -40实施例10*            7.9               157             -42对比例对比例1               3.87              130             ＜-65对比例2               5.51              135             ＜-65对比例3               5.06              147             -18对比例4               4.00              114             -15对比例5               6.94              102             -15对比例6               150               214             -42*本发明的实施例
图1为典型的加氢处理的烃类润滑油基础油(XHVI)和本发明的两种基础油的冷起动模拟(CCS)性能的比较图。CCS试验按ASTM法D5392进行，它用来测量车用机油的表观粘度。CCS粘度计在低温和低剪切速率和应力下测量流体的动态粘度，从而模拟油品在低温起动(曲轴)条件下、在发动机曲轴箱中的流动。图1的数据证明，本发明的润滑油基础油具有更好的低温粘度性质。分支特性的测量
分支指数(BI)
对于表1所列的每种基础油，使用10％的CDCl3溶液，在Bruker360MHz AMX光谱仪上得到359.88 MHz 1H溶液NMR谱。TMS为化学位移内参比。CDCl3溶剂在7.28处有一峰。所有谱图都在90度脉冲(10.9微秒)、脉冲延迟时间为30秒，它至少是最长的氢自旋晶格松弛时间(T1)的5倍和120扫描的定量条件下得到，以确保良好的信噪比。按以下的范围确定H原子的类型：
9.2-6.2ppm在芳环上的氢；
6.2-4.0ppm在烯属碳原子上的氢；
4.0-2.1ppm在芳环α位的苄基氢；
2.1-1.4ppm烷属CH次甲基氢；
1.4-1.05ppm烷属CH2亚甲基氢；
1.05-0.5ppm烷属CH3甲基氢。
分支指数(BI)作为在0.5-1.05ppm范围内的非苄基的甲基氢的百分数与在0.5-2.1ppm范围内的总非苄基的脂族氢的比来计算。由这些1H NMR分析得到的结果汇于下表2。
                         表2
             由1H NMR得到的不同类型氢的百分数说明                   ％CH3         ％CH2       ％CH        BIParaflintC80蜡(进料)实施例1                 19.4           78.5         2.1       19.4实施例2                 22.3           76           1.7       22.3实施例3                 25.6           71.8         2.6       25.6实施例4*               27.6           68.1         4.3       27.6SMDS含蜡抽余油(进料)    10.3           89.7         0         10.3实施例5                 23.6           70.1         6.3       23.6实施例6*               29.8           67.8         2.4       29.8实施例7*               26.2           71.2         2.6       26.2实施例8*               30             67           3         30实施例9*               27.9           69.9         2.2       27.9实施例10*              27             70.8         2.2       27对比例对比例1                 22.7           74.8         2.5       22.7对比例2                 23.4           74.3         2.3       23.4对比例3                 26.9           69.4         3.7       26.9对比例4                 30.0           61.9         8.1       30.0对比例5                 31.5           55.3         13.2      31.5对比例6                 19.4           78.7          1.9      19.4
*本发明的实施例
分支接近度(CH2＞4)
对于表1所列的每种基础油，使用10％的CDCl3溶液，在Bruker 360MHz AMX光谱仪上得到90.5MHz 13C NMR信号脉冲和135不失真增强极化传递(DEPT)NMR谱图。TMS为化学位移内参比。在13C谱图中，CDCl3溶剂在77.23ppm处有三重峰。所有的信号脉冲谱图都在以下定量条件下得到：使用45度脉冲(6.3微秒)、脉冲延迟时间为60秒，它至少为最长的碳自旋晶格松弛时间(T1)的5倍，以确保样品的完全松弛，以及200扫描以确保良好的信噪比和WALTZ-16质子去偶合。
由135DEPT 13C NMR实验来确定碳原子类型CH3、CH2和CH。在所有13C NMR谱中～29.8ppm处的主要CH2共振是由于等价重复亚甲基碳，它们为离末端基团或分支4个或4个以上的亚甲基(CH2＞4)。对于在分支末端的甲基碳或离分支上甲基一个亚甲基的亚甲基碳，主要根据13C化学位移来测定分支的类型。用CH2＞4表示的分支接近度和碳的类型汇于表3。
                        表3
             由13C NMR得到的不同类型碳的百分数说明                  ％CH3   ％CH2   ％CH    ％CH2＞4ParaflintC80蜡(进料)实施例1               13.6      81.3     5.1      38.2实施例2               15.7      78.6     5.7      28.8实施例3               17.3      76.3     6.3      22.5实施例4*             18        75.5     6.5      14.7SMDS含蜡抽余油(进料)  6.2       93.8     0        58.8实施例5               16.6      77.3     6        17.3实施例6*             24.9      67.4     7.7      7.7实施例7*             16.4      77.5     6.1      21.8实施例8*             19.3      75.1     5.6      12.8实施例9*             18.1      76.3     5.6      17.7实施例10*            15.9      76.3     7.7      20.5对比例对比例1               11.4      83.7     4.9      20.4对比例2               13.2      81       5.8      20.6对比例3               19        74.3     6.7      22.6对比例4               16.7      72.3     11       20.4对比例5               16.5      62      21.5      19.2对比例6
                  12.3      83.9     3.8      17.3
*本发明的实施例
如表1-3中公开的，例证性基础油的异构烷烃组分的分支特性和倾点在下表4中进行了比较。
                          表4
                异构烷烃润滑油组合物的比较说明                      BI       ％CH2＞4       倾点℃ParaflintC80蜡(进料)                               83实施例1                  19.4        38.2          12实施例2                  22.3        28.8          -3实施例3                  25.6        22.5         -24实施例4*                27.6        14.7         -63SMDS含蜡抽余油(进料)     10.3        58.8          39实施例5                  23.6        17.3         -24实施例6*                29.8         7.7         -66实施例7*                26.2        21.8         -18实施例8*                30          12.8         -59实施例9*                27.9        17.7          40实施例10*               27          20.5         -42对比例对比例1                  22.7        20.4        ＜-65对比例2                  23.4        20.6        ＜-65对比例3                  26.9        22.6          -18对比例4                  30.0        20.4          -15对比例5                  31.5        19.2          -15对比例6                  19.4        17.3          -42*本发明的实施例
本发明的基础油可用BI表示的分支程度和用CH2＞4表示的分支接近度与其他的烃类基础油区分开。这些组成指纹用图表示有助于在如图2所说明的2维组成空间确定极好的范围(左象限)。
从图2可清楚看出，本发明的异构烷烃基础油组合物的分支特性在极好的范围内。具体地说，可将该组合物描述为含有异构烷烃组分的混合物，其中用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85  (CH2＞4)＜45。
图3为包括本发明的在内的各种烃类流体的动态粘度(DV@-40℃，用CCS法测量)和动力粘度(KV@100℃)的比较图。本发明的流体表示为“FTWI”(费托合成蜡的异构化油)，而那些传统的加氢裂化油表示为“HDC”。具体地说，HDC数据点代表本说明书的对比例3-5。
从图3所示的数据可清楚看出，与现有技术的传统HDC流体相比，本发明的FTWI流体有好得多的低温粘度特性。应当指出，本发明的所有液体烃类流体都在图中虚线以下，所以可用以下方程式来描述：
(c)DV@-40℃＜2900(KV@100℃)-7000。
虽然如此描述了本发明，显然可用许多方式作出某些改变。不认为这样的改变背离了本发明的精神实质和超出了本发明的范围；对于熟悉本专业的技术人员来说，所有这些改变都是显而易见的，打算将所有这些改变包括在以下权利要求书的范围内。

Claims (21)

1.一种含有烷烃组分的液体烃类组合物，其中对所述的液体烃类组合物作为整个测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
2.根据权利要求1的液体烃类组合物，它含有：＜0.1％(重量)芳烃；＜20ppmW含氮化合物和＜20ppmW含硫化合物。
3.根据权利要求1的液体烃类组合物，其中组合物的倾点小于-18℃。
4.根据权利要求3的液体烃类组合物，其中组合物的倾点小于-30℃。
5.根据权利要求1的液体烃类组合物，其中所述的烷烃组分的BI≥25.4和(CH2＞4)≤22.5。
6.根据权利要求1的液体烃类组合物，其中所述的烷烃组分的正常沸点为370C+。
7.根据权利要求1的液体烃类组合物，其中所述的烷烃组分每100个碳原子平均含有10个己基或更长的分支。
8.根据权利要求1的液体烃类组合物，其中所述的烷烃组分每100个碳原子平均含有16个以上甲基分支。
9.根据权利要求1的液体烃类组合物，其中所述的液体烃类流体的用CCS法测量的-40℃动态粘度和100℃下测量的动力粘度的组合可用下式表示：
(c)DV@-40℃＜2900(KV@100℃)-7000。
10.一种含有烷烃组分的润滑油基础油组合物，其中对所述的润滑油基础油组合物作为整体测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支有4个或4个以上碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45。
11.根据权利要求10的润滑油基础油组合物，它含有：＜0.1％(重量)芳烃；＜20ppmW含氮化合物和＜20ppmW含硫化合物。
12.根据权利要求10的润滑油基础油组合物，其中组合物的倾点小于-18℃。
13.根据权利要求12的润滑油基础油组合物，其中组合物的倾点小于-30℃。
14.根据权利要求10的润滑油基础油组合物，其中所述的烷烃组分的BI≥25.4和(CH2＞4)≤22.5。
15.根据权利要求10的润滑油基础油组合物，其中所述的烷烃组分的正常沸点为370C+。
16.根据权利要求10的润滑油基础油组合物，其中所述的烷烃组分每100个碳原子平均含有小于10个己基或更长的分支。
17.根据权利要求10的润滑油基础油组合物，其中所述的烷烃组分每100个碳原子平均含有16个以上甲基分支。
18.根据权利要求10的润滑油基础油组合物，其中所述的液体烃类流体用CCS法在-40℃下测量的动态粘度和100℃下测量的动力粘度的组合用下式表示：
(c)DV@-40℃＜2900(KV@100℃)-7000。
19.一种润滑油组合物，它含有烷烃组分混合物的液体烃类组合物，其中对所述液体烃类组合物作为整体测量的用甲基氢的百分数量度的分支程度(BI)和用离末端基团或分支4个或4个以上亚甲基碳的重复亚甲基碳的百分数量度的分支接近度(CH2＞4)是这样的：
(a)BI-0.5(CH2＞4)＞15；以及
(b)BI+0.85(CH2＞4)＜45；以及任选的选自抗氧化剂、抗磨添加剂、极压添加剂、摩擦改进剂、粘度指数改进剂、降凝剂、清净剂、分散剂、腐蚀抑制剂、金属钝化剂、密封相容性添加剂、抗乳化剂、抗泡沫剂及其混合物的有效数量的润滑油添加剂。
20.根据权利要求19的润滑油组合物，它还含有选自矿物油、聚α烯烃、酯类、聚链烯烃、烷基化的芳烃、加氢裂化油和溶剂精制基础油的润滑油基础油。
21.根据权利要求20的润滑油组合物，其中所述的液体烃类组合物的浓度为总润滑油基础油组合物的至少5重量％。
CNB988112280A 1997-10-20 1998-10-15 异构烷烃润滑油基础油组合物 Expired - Lifetime CN1138848C (zh)

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