CN100510032C - 用作重质润滑剂基础原料的重质烃组合物 - Google Patents
用作重质润滑剂基础原料的重质烃组合物 Download PDFInfo
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Abstract
用作重质烃基础原料的重质烃组合物,包括至少为95wt%的链烷烃分子,其中至少90wt%是异链烷烃,包括具有连续数量碳原子的烃分子,为在100℃时根据ASTM D-445测量的运动粘度大于8cSt的液体,其初始沸点至少为850℉(454℃),终沸点至少为1,000℉(538℃),所述异链烷烃分子,根据甲基氢百分比测量的异链烷烃分子的支化系数(BI)、根据从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比测量的支化接近度(CH2>4),是这样的要使得重质烃组合物作为整体测量如下:(a)BI-0.5(CH2>4)<15;及(b)BI+0.85(CH2>4)<45。
Description
公开背景
发明领域
本发明涉及一种通过异构化Fischer-Tropsch蜡制得的用作重质润滑剂基础原料的重质烃组合物,还涉及重质润滑剂基础原料以及由基础原料形成的重质润滑剂。
发明背景
重质润滑剂用于高粘度应用中,其中基于轻质油的润滑剂不能在运动部件间提供足够的润滑作用,如重质机油、齿轮组、深冲压油及手工传输。重质润滑剂是通过化合重质润滑剂基础原料形成,该基础原料是有润滑油性质的重质油,其包括一种或多种润滑剂添加剂。大部分重质润滑剂基础原料源自天然生成的石油,并含有芳香不饱和物,包括多核芳香物以及含硫和含氮化合物。这些化合物有降低油和重质润滑剂的粘度和稳定性的趋势。精制油来除去这些成分会导致产物油的低产率。重质链烷烃可被精制成低水平不饱和物和杂原子化合物,但却有不可接收的高倾点和浊点。
需要相对纯净或高品质的重质烃组合物,其至少在使用温度下为液体,并用作重质润滑剂基础原料或在其中使用。
美国专利6,090,989(Trewella等)公开了链烷烃成分的液体烃组合物,其中根据甲基氢百分比测量的分支程度(BI)、根据从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比测量的支化接近度(CH2>4),使得根据液体烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)>15;及
(b)BI+0.85(CH2>4)<45。
美国专利6,090,989的基础原料的特征为极低倾点(PP),小于或等于-18℃,且在100℃时其运动粘度优选约为4cSt~8cSt。虽然美国专利6,090,989的组合物作为润滑剂基础原料有优良的作用,但是某些应用需要使用重质润滑剂,特别是在100℃时其运动粘度大于8cSt。这通常需要在基础原料中存在相对长链的烃分子。然而,提高烃混合物中的烃分子链长度通常会使倾点和浊点增大,这是不需要的。可选择地,添加剂如粘度指数改进剂及倾点和浊点下降剂可被用于使润滑剂具有所需的性能。使用添加剂除了成本较高外,添加剂易于随使用变质。因此,本发明的目的是提供一种组合物,其具有相对较高的粘度、较好的润滑度和氧化稳定性,但是低倾点和浊点。
此外,经常需要有用的烃组合物,例如在化学和药品制造中等作为重质白油、药用油、载体或医用制剂的底物。这种应用通常需要纯净且化学惰性的原料,例如其不会在药物应用中产生敏感性。换言之,需要烃组合物,其芳香物和含杂原子成分的含量非常低。
本发明提供一种具有高粘度及低倾点和浊点的重质烃组合物。
发明概述
本发明涉及一种相对纯净、高质量的重质烃组合物,其用作重质润滑剂基础原料或在其中使用,涉及一种重质润滑剂基础原料,还涉及一种由重质润滑剂基础原料形成的重质润滑剂。
重质烃组合物主要包括(例如≥98wt%)饱和的链烷烃分子,其是在100℃时运动粘度大于8cSt(厘沲)的液体,其初始(5%)沸点至少为850℉(454℃),终端(95%)沸点至少为1,000℉(538℃)。重质烃组合物包括至少为95wt%的链烷烃分子,其中至少90wt%是异链烷烃。根据本发明,异链烷烃占重质烃组合物的链烷烃分子的至少90wt.%。重质烃组合物包括具有连续数量的碳原子的烃分子。所述异链烷烃分子根据甲基氢百分比测量的异链烷烃分子的分支程度(在下文中称为支化系数(BI))、根据从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比测量的支化接近度(CH2>4),使得根据重质烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)<15;及
(b)BI+0.85(CH2>4)<45。
重质烃组合物用作重质润滑剂基础原料或在其中使用。
支化接近度(CH2>4)说明了烃中链烷烃分子的正链烷烃特征。通常,为获得较高的润滑度,需要含有相对高的正链烷烃特征的链烷烃分子的组合物,即少量的分支和/或短分支。然而,具有相对较高的正链烷烃特征的链烷烃会给出不需要的倾点和浊点,因为正链烷烃在较高温度下易于从链烷烃混合物中结晶出来。
根据甲基氢百分比测量的支化系数是与骨架连接的分支数量的度量。如果由大量的分支且分支主要是甲基,那么支化系数较大。
例如,给定一定总数的碳原子,在相对短的骨架上具有大量分支和长分支即较小的正链烷烃特征的链烷烃分子具有相对较小的支化接近度(CH2>4)。具有相同总数的碳原子但有少量的彼此间或与端基的距离较大的链烷烃分子且骨架相对较长即具有更多正链烷烃特征的链烷烃分子具有相对较大的支化接近度(CH2>4)。
美国专利6,090,989涉及一种液体烃组合物,其中BI-0.5(CH2>4)>15。目前令人惊讶地发现如果(a)BI-0.5(CH2>4)<15,那么可获得具有相对高粘度而低倾点和浊点的重质烃组合物。换言之,根据本发明,与美国专利6,090,989所列举的组合物相比,支化接近度(CH2>4)较大。这种发现是意外的,因为本发明的重质烃组合物含有具有更大正链烷烃特征(这由相对大的支化接近度说明)的链烷烃分子,且仍具有低倾点和浊点。事实上,这种发现与低倾点和浊点需要较小的正链烷烃和较大的异链烷烃特征的普通认识相反。
BI优选小于24,支化接近度(CH2>4)优选大于17。
在另一个实施方案中,本发明涉及一种通过使本发明的重质润滑剂基础原料与一种或多种润滑剂添加剂混合而形成的重质润滑剂。尽管本发明的重质烃组合物用作重质润滑剂基础原料,但是也可以有其他用途,例如在化学和药品制造中等作为重质白油、药用油、载体或医用制剂的底物。因此在另一个实施方案中,本发明包括一种或多种下面的重质烃组合物,或其中至少部分使用或基于本发明的重质烃组合物;在化学和药品制造方法中作为重质白油、药用油、载体或医用制剂的底物。
在另一个实施方案中,本发明涉及一种包括本发明的重质烃组合物的基础原料。换言之,本实施方案涉及重质烃组合物在基础原料中或作为基础原料的用途。优选地,本发明的基础原料由重质烃组合物组成。
附图简述
附图是根据本发明的重质烃组合物、申请的比较例的NMR光谱、及上述包括其他烃组合物的美国专利6,090,989的数据绘制的BI和%CH2>4值的曲线图。美国专利6,090,989的公开在此全部引为参考。图中的阴影面积表明本发明的重质烃组合物的NMR参数空间。仅有优选源于从Fischer-Tropsch合成的含蜡烃和PAO基础原料的本发明的重质烃组合物落于该参数空间内。PAO原料的分子组合物与本发明的重质烃组合物区别在于:(i)其不包括具有连续数量碳原子的烃分子,(ii)在分子中源于CH3的氢原子的百分比小于15,然而本发明的重质烃组合物的优选大于20,(iii)源于PAO原料的CH的氢原子的百分比优选大于3,然而本发明的重质烃组合物的优选小于2。
详细说明
本发明提供包括至少95wt%链烷烃分子的重质烃组合物,其中至少90wt%是异链烷烃,包括有连贯数量碳原子的烃分子,该重质烃组合物包括具有连续数量的碳原子的烃分子,且在100℃时是液体,在该温度下其运动粘度大于8cSt(ASTM D-445),初始沸点和终沸点分别至少为850和1000℉(454和538℃),其中根据甲基氢百分比测量的支化系数(BI)、根据从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比测量的支化接近度(CH2>4),使得根据重质烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)<15;及
(b)BI+0.85(CH2>4)<45。
优选地,本发明的重质烃组合物从Fischer-Tropsch蜡制得,主要包括(≥98wt%)饱和的链烷烃,其中至少90wt%是非环烃,环烃不超过10wt%。链烷烃分子的至少90、优选至少95wt%、更优选至少98wt%、最优选至少99wt%是异链烷烃。而如果存在,链烷烃的环烃量可达5wt%,更通常不超过1wt%。
在100℃下根据ASTM D-445测量的本发明的重质烃组合物的运动粘度大于8cSt。本发明的重质烃组合物含有连续数量碳原子的分子,并优选至少95wt%为C30+烃分子。初始沸点至少为850℉(454℃),优选为900℉(482℃),终沸点至少为1,000℉(538℃)。重质烃组合物通常在温度和压力条件下为液体,通常但不总是在75℉(24℃)和1个大气压(101kPa)的环境条件下。初始和终沸点值是额定的,指使用下述方法通过气相色谱蒸馏(GCD)得到的T5和T95馏份(沸腾温度)。
根据甲基(CH3)氢百分比测量的异链烷烃成分的分支程度或支化系数(BI),及根据从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比测量的支化接近度(CH2>4),使得根据重质烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)<15;及
(b)BI+0.85(CH2>4)<45。
BI优选小于24(BI>24),支化接近度优选大于17((CH2>4)>17)。重质烃组合物也优选含有至少75wt%的C35+烃分子。
本发明的重质烃组合物不同于从美国专利6,090,989公开的石油、散蜡、PAO油和润滑剂基础原料得到的那些,其通过异构化Fischer-Tropsch蜡得到。
含有硫、氮和金属的烃化合物形式的硫、氮和金属其量小于50wppm。从Fischer-Tropsch蜡制得的本发明的重质烃组合物通常含有小于1wppm的硫、氮和金属。这些可通过X-射线或Antek氮测试来检测。
尽管本发明的重质烃组合物是各种分子量链烷烃的混合物,但氢化脱蜡后残余的正链烷烃含量小于5wt%,更通常小于1wt%,至少95%的油分子含有至少一种分支,至少一半是甲基分支。至少一半、更优选至少75%的其余分支是乙基,小于25%、优选小于15%的总分支具有3个或更多个碳原子。分支碳原子的总数通常占烃分子包括的碳原子总数的小于25%、优选小于20%、更优选不超过15%(例如10-15%)。
PAO油是偶数碳的线性α烯烃的低聚产物,通常是1-癸烯。因此PAO油分子包括偶数碳烃分子的混合物,碳原子数量彼此不同,是线性α烯烃起始单体中的碳原子数的倍数。即使具有偶数个碳原子(例如癸烯和十二烯)的低聚线性α烯烃单体的混合物以形成重质润滑剂基础原料,那么生成的烃分子中的碳原子数仍具有偶数个碳原子。这一点不同于本发明的重质烃组合物的连续数量烃分子的混合物,其偶数和奇数个碳原子的包括烃分子,连续碳原子的数量彼此不同(例如1、2、3、4、5、6、7和更多个碳原子)。
本发明重质烃组合物的烃分子连续数量碳原子彼此不同,这是Fischer-Tropsch烃合成反应的结果,其中异构化蜡物料以形成本发明的重质烃组合物。尽管优选的重质烃组合物从合成源制得,而不是从矿物油源制得,因而可以称为合成重质烃组合物,但本发明的重质烃组合物不限于基于合成源。然而,在优选的实施方案中,重质烃组合物基于合成源,更优选基于Fischer-Tropsch产物。
在Fischer-Tropsch烃合成反应中,碳原子源是CO,烃分子同时积聚在一个碳原子上。与基于PAO的油相比,本发明重质烃组合物的烃分子具有更线性的结构,包括相对较长的骨架,较短和较少的分支。经典教材对PAO的说明是一种星形分子,尤其是十三烷,其被表示为与中心点连接的3个癸烷分子。尽管理想星形分子是理论上的,然而PAO分子比构成本发明基础原料的烃分子具有较少和更长的分支。
因此,构成本发明的重质烃组合物的分子优选包括具有相对线性分子结构至少95wt%的异链烷烃(不超过5wt%的饱和环),小于一半的分支具有两个或更多个碳原子,分支中的碳原子总数小于25%。与本发明相比,在构成PAO油的分子中,多于一半的分支具有两个或更多个碳原子,分支中的碳原子总数小于25%。
本领域所属技术人员知道,润滑剂基础原料有时也称为润滑油基础原料,包括重质润滑剂基础原料,是一种在润滑油沸程内沸腾的油,其具有润滑性能并用于制备各种润滑剂如润滑油和油脂。在本发明中,重质烃组合物在重质润滑油沸程内沸腾。最终形成的重质润滑剂或重质润滑油可通过将有效量的至少一种添加剂加到重质润滑剂基础原料中制得,更通常是加入含有多于一种添加剂的添加剂组。这种添加剂示例性但非限制实例包括一种或多种洗涤剂、分散剂、抗氧化剂、抗磨添加剂、极压添加剂、倾点下降剂、VI改进剂、摩擦改性剂、脱乳剂、抗氧化剂、消泡剂、腐蚀抑制剂及密封溶胀控制添加剂。
本发明的重质烃组合物优选包括脱蜡的油,并具有低温性能可以满足所需的规格或要求,在使用的温度和压力条件下也是透明的油状液体。通常但不总是,在室温75℉(24℃)和压力条1个大气压(101kPa)件下是油状液体,在此压力和100℃温度下是油状液体。在某些情况下,浊点可以高于75℉(24℃)。根据本发明制备的本发明的重质烃组合物其终沸点高于1,250℉(677℃),浊点和倾点分别为1℃和-31℃。重质润滑剂基础原料和精制的重质润滑剂的低温性能需求可以变化,并取决于其应用和其应用的地理位置。通过形成本发明的重质润滑剂基础原料和有效量的至少一种添加剂或更通常上述含有多于一种添加剂的添加剂组的混合物来制备重质润滑剂组合物。用于形成混合物的本发明的重质润滑剂基础原料通常在氢化脱蜡后已被温和加氢精制和/或去浊,以提高其颜色、外观和稳定性。
公知的是,混浊是指阴暗或不清晰,是一种外观因素。通常通过催化或吸附方法除去这些引起混浊的要素可实现去浊。加氢精制是极温和、相对冷的氢化方法,其使用催化剂、氢和温各反应条件以除去痕量原子化合物、芳香物和烯烃,以提高氧化稳定性和颜色。加氢精制反应条件包括温度为302~662℉(150~350℃)并优选为302~482℉(150~250℃),总压力为400~3000psig(2859~20786kPa),液体按小时计空速为0.1~5LHSV(hr-1)并优选为0.5~3hr-1。氢计处理气速率为2550~10000scf/B(44.5~1780m3/m3)。催化剂包括载体成分和至少一种催化金属成分,金属为第VIB族(Mo,W,Cr)和/或铁族(Ni,Co)和第VIII族的贵金属(Pt,Pd)。第VIB族和第VIII族指在Sargent-Welch元素周期表(由Sargent-Welch Scientific Company于1968年出版)中的第VIB族和第VIII族。对于贵金属而言金属可为催化剂组合物的0.1wt.%,对非贵金属而言可为30wt.%。优选的载体材料是低酸度的,包括例如无定形或晶体金属氧化物如氧化铝、二氧化硅、二氧化硅氧化铝和被称为介孔晶体材料的超大孔晶体材料,其中MCM-41是优选的载体成分。MCM-41的制备和用途是公知的,并公开于例如美国专利5,098,684、5,227,353和5,573,657中。
含蜡物料或Fischer-Tropsch蜡包括在Fischer-Tropsch烃合成反应器中制得的含蜡烃馏份,其在反应条件下是液体。由于其在75℉(24℃)和1个大气压(101kPa)下是固体,所以称为蜡。必须含有足量在高于1000℉(538℃)沸腾的含蜡材料,以制备本发明的重质烃组合物。含蜡物料通常在一个或多个催化脱蜡步骤中脱蜡,其中物料在脱蜡条件下与氢接触和脱蜡催化剂接触。通过对含有分子达到20个碳原子的组合物进行GC-FID、对含有≥20个碳原子的分子的组合物进行GC-FID和13C-NMR来测量异链烷烃与正链烷烃比。芳香物通过公开于ASTM标准D-2622中的X-射线荧光(XRF)确定。根据ASTM标准D-2622由XRF测定硫,根据ASTM标准D4629通过注射/进入氧化燃烧及化学发光检测来测定氮。
氢化脱蜡步骤中所用的催化剂包括固体酸成分、氢化成分和粘合剂。用于氢化脱蜡的适合催化剂成分的示例性但非限制性实例包括例如ZSM-23、ZSM-35、ZSM-48、ZSM-57、ZSM-22(也称为θ-1或TON)及二氧化硅铝硅酸盐(被称为SAPO’s(例如SAPO-11、31和41)、SSZ-32、沸石β、发光沸石和稀土离子交换的镁碱沸石。也可使用氧化铝和无定形二氧化硅氧化铝。
在许移其他沸石催化剂下,需要时可以将固体酸成分与基质材料(也称为粘合剂)混合,基质材料对脱蜡方法中使用的温度和其他条件具有耐性。这种基质材料包括活性和非活性材料,合成或天然沸石,及无机材料如粘土、二氧化硅和/或金属氧化物例如氧化铝。后者可以是天然或凝胶沉淀物、溶胶或凝胶形式,包括二氧化硅和金属氧化物的混合物。混合有固体酸成分的材料的用途,即混合具有活性,可以增强催化剂的转化和/或选择性。非活性材料适于用作稀释剂以控制在给定方法中的转化量,使得可经济有序地得到产物,而不需使用控制速率或反应的其他装置。通常,晶体硅酸盐材料被加到天然粘土中,例如斑脱土和高岭石。这些材料即粘土、氧化物等部分地用作催化剂粘合剂。优选提供具有良好压碎强度的催化剂,这是由于在石油精制中催化剂经常需要严格处理,使催化剂成为粉末状材料,从而在处理中产生问题。
可与固体酸成分复合的天然粘土包括蒙脱石和高岭石族,其包括亚斑脱土、通常称为Dixie、McNamee、Georgia和Florida粘土的高岭石、其中主要矿物成分是多水高岭石、高岭石、地开石、珍珠陶土或富硅高岭石的其他物质。这种粘土可以以原始开采的粗态使用,或以经过煅烧、酸处理或化学改性的形式使用。
除了上述材料外,固体酸成分可与下述材料混合:多孔基质材料如二氧化硅-氧化铝,二氧化硅-氧化镁,二氧化硅-氧化锆,二氧化硅-氧化钍,二氧化硅-氧化铍,二氧化硅-二氧化钛,及三元组合物如二氧化硅-氧化铝-氧化钍,二氧化硅-氧化铝-氧化锆,二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。基质可以是共凝胶形式。也可使用这些成分的混合物。精细分散的固体酸成分和无机氧化物凝胶基质的相对比例可随晶体硅酸盐含量变化,约为复合体的1~90wt%,更通常约为2~80wt%。优选使用ZSM-48。
氢化成分包括至少一种第VIII族金属成分并优选至少一种第VIII族贵金属成分,如Pt和Pd。贵金属浓度按催化剂总重计约为0.1-5wt%的金属,更通常约为0.2-1wt%,包括ZSM-48沸石成分和用于催化剂复合体中的任何粘合剂。第VIII族指在Sargent-Welch元素周期表(由Sargent-Welch Scientific Company于1968年出版)中的第VIII族。
ZSM-48(ZSM-48沸石包括在结构上等效的EU-2、EU-11和ZBM-30)的制备是公知的并公开于例如美国专利4,397,827;4,585,747和5,075,269及EP 0 142 317中,其公开内容在此引入作为参考。用于本发明中的其他氢化脱蜡催化剂包括主要通过异构化而不是裂解或氢化裂解脱蜡的任何公知的催化剂。包括10和12元环结构的沸石用作脱蜡催化剂,尤其当与催化金属氢化成分混合时。用于制备本发明的烃或重质润滑剂组合物的氢化脱蜡反应条件包括温度、氢分压和空速分别为450-750℉(232-399℃)、10-2,000psig(69-13790kPa)和0.1-5.0LHSV。这些条件通常可变为500-700℉(260-371℃)、100-1000psig(690-6895kPa)和0.5-3.0LHSV,压力优选为200-700psig(1379-4827kPa)。
实施例
实施例1
在本实施例中,蜡物料包括全部430℉+(221℃)含蜡烃馏份,并在在含有二氧化钛支撑的铼助催化的非迁移钴烃合成催化剂的浆料Fischer-Tropsch烃合成反应器中制得。蜡包括至少为90wt%的正链烷烃和26.2wt%的1000℉+(538℃)馏份。在含有Pt贵金属成分的ZSM-48氢化脱蜡催化剂的存在下用氢氢化脱蜡以形成异构物。分馏异构物除去700℉-(371℃-)烃,然后分馏剩余的700℉+(371℃+)馏份以除去并回收950℉+(510℃+)重质润滑剂异构物馏份。然后重质异构物馏份在分开的反应器中用相同的ZSM-48氢化脱蜡催化剂进一步用氢氢化脱蜡,以形成重质烃组合物或本发明的重质润滑剂基础原料。在第一和第二反应器中的氢化脱蜡条件包括温度分别为586℉(308℃)和616℉(324℃),低氢压力为250psi(1724kPa)。这些组合物的性能列于下面表中,在100℃时其运动粘度为13和15cSt。
在两个反应器中的ZSM-48氢化脱蜡催化剂包括在氢形式的ZSM-48沸石和氧化铝粘合剂复合体上的0.6wt.%的Pt作为氢化成分。根据美国专利5,075,269中的方法制备催化剂的氢形式的ZSM-48沸石,该专利内容在此引入作为参考。使用公知方法,通过浸渍、然后烧结和还原加入Pt成分。
使用ASTM D-5307的高温GCD方法的改进进行气相色谱蒸馏(GCD)。柱由具有薄液体相的单毛细管柱构成,小于0.2微米。使用外部标准,由5~100个碳的沸点校准曲线组成。使用温度控制的注射器,在注射前样品用热水温和加热。使用该方法及T5和T95 GCD结果测定沸程。使用ASTM D-5773通过Phase Two Tec Instruments按润滑剂过程方法测量浊点值。根据ASTM D-5950对ISL自动倾点的测量测定倾点。下表中的浊点和倾点以℃为单位。分别根据ASTM协议D-445和D-2270测定粘度和粘度指数。
实施例2
在本实施例中,蜡物料是商业上可得到的Paraflint C-80,其是通过在固定床Fischer-Tropsch反应器中用迁移铁催化剂用Sasol制备的加氢处理的Fischer-Tropsch蜡。未处理的粗蜡含有相对较高水平的芳香和脂肪族不饱和物及杂原子化合物,其被加氢处理以制备ParaflintC-80蜡。固体蜡是在100℃时粘度为6-10cSt和额定T5沸点约为850℉(454℃)的蒸馏馏份。与上述相似在已被硫化的PT/ZSM-48催化剂存在下在单一反应器中用氢氢化脱蜡。氢化脱蜡反应压力为1000psi(6895kPa)。通过蒸馏使氢化脱蜡产物分馏,得到本发明的重质烃组合物,在100℃时其粘度为11cSt at,其性能如下表所示。
比较例A
此实验与实施例1的相似,除了700-950℉(371-510℃)异构物在分开的反应器中用ZSM-48氢化脱蜡催化剂用氢进一步氢化脱蜡,以形成非本发明的组合物,在100℃时其粘度为4cSt。在第一和第二反应器中氢化脱蜡条件包括温度分别为586℉(308℃)和597℉(314℃),低氢压力为250psi(1724kPa)。比较组合物显示于表中。
比较例B
在物料、催化剂和单独氢化脱蜡反应器方面与实施例2相似。在100℃时其粘度为6和8cSt的两个组合物通过蒸馏分馏氢化脱蜡的产物得到。这两个组合物都不是本发明的组合物,为比较列于下表中。
*因CH3、CH2及CH氢的1H(质子)共振的强度百分比
**从端基或分支除去的4个或更多个碳的重复亚甲基碳的百分比
用碳-13NMR光谱分析表中组合物的微结构。在用7.5mg/mlCr(acac)3掺杂的氯仿-d中制备w/w浓度为20-25%的样品。用TMS设置到0.0ppm进行化学迁移参考。用Varian Unity Plus 500得到光谱,碳Larmor步骤为125.7MHz,每个光谱8000个共平均瞬态。所有光谱在碳可逆栅极WALTZ-16退耦上具有90°激发脉冲(在0.8秒的收集时间内),再循环延迟为6秒。在50℃下制备样品和数据收集。选择数据收集参数(铬掺杂,延迟,可逆栅极退耦)以确保精确和定量积分。关于NMR技术、数据收集和计算,可以参考美国专利6,090,989。
将约80mg样品溶解在1gm氯仿-d中,用5mm可切换的探针对样品进行质子NMR分析。样品制备和数据收集用Varian Unity Plus500在50℃下进行。使用90°激发脉冲得到64个共平均瞬态的自由感应延迟,延迟为8.4秒,收集时间为3.2秒。在质子NMR中未使用延迟试剂。
这些数据表明本发明的重质烃组合物(粘度为11、13和15cSt)包括如下分子:其中支化系数(BI),及支化接近度(CH2>4),使得根据重质烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)<15;及
(b)BI+0.85(CH2>4)<45。
此外,数据表明本发明的重质烃组合物,其BI通常小于25,支化接近度(CH2>4)通常大于17。
附图是根据本发明的重质烃组合物、申请的比较例的NMR光谱、及包括其他烃组合物的美国专利6,090,989的数据绘制的BI和%CH2>4值的曲线图。美国专利6,090,989的公开在此全部引为参考。图中的阴影面积表明本发明的重质烃组合物的NMR参数空间。仅有优选源于从Fischer-Tropsch合成的含蜡烃和PAO基础原料的本发明的重质烃组合物落于该参数空间内。PAO原料的分子组合物与本发明的重质烃组合物区别在于:(i)其不包括具有连续数量碳原子的烃分子,(ii)在分子中源于CH3的氢原子的百分比小于15,然而本发明的重质烃组合物的优选大于20,(iii)源于PAO原料的CH的氢原子的百分比优选大于3,然而本发明的重质烃组合物的优选小于2。
Claims (19)
1.一种重质烃组合物,包括至少为95wt%的链烷烃分子,其中至少90wt%是异链烷烃,包括具有连续数量碳原子的烃分子,其是在100℃时根据ASTM D-445测量的运动粘度大于8cSt的液体,其初始沸点至少为850℉(454℃),终沸点至少为1,000℉(538℃),其中所述异链烷烃分子根据甲基氢百分比测量的异链烷烃分子的支化系数(BI)、根据从端基或分支除去的4个或更多个碳原子的重复亚甲基碳的百分比测量的支化接近度(CH2>4),是这样的要使得重质烃组合物作为整体测量如下:
(a)BI-0.5(CH2>4)<15;及
(b)BI+0.85(CH2>4)<45。
2.如权利要求1所述的组合物,其中所述支化系数(BI)小于24,所述组合物含有至少95wt%的具有至少30个碳原子的烃分子。
3.如权利要求2所述的组合物,其中所述支化接近度(CH2>4)大于17。
4.如权利要求3所述的组合物,其中所述异链烷烃分子小于一半的分支具有两个或更多个碳原子。
5.如权利要求4所述的组合物,其中在所述异链烷烃分子中小于25%的碳原子总数在所述分支中。
6.如权利要求5所述的组合物,包括至少98wt%饱和的链烷烃,其中至少90wt%是非环烃,环烃不超过5wt%。
7.如权利要求6所述的组合物,其中小于25%的所述总分支数具有三个或更多个碳原子。
8.如权利要7所述的组合物,其中小于15%的所述总分支数具有三个或更多个碳原子。
9.如权利要求8所述的组合物,其终沸点高于1050℉(566℃)。
10.如权利要求9所述的组合物,包括至少95wt%的烃具有30个或更多个碳原子。
11.如权利要求10所述的组合物,其T5沸点至少为900℉。
12.如权利要求8所述的组合物,其中在所述异链烷烃分子中小于25%的碳原子总数在所述分支中。
13.如权利要求12所述的组合物,其已被加氢精制并可选择地去浊。
14.如权利要求13所述的组合物,其在75℉(24℃)和1个大气压(101kPa)的条件下是液体。
15.如权利要求1所述的组合物,其是合成组合物。
16.如权利要求3所述的组合物,在一种或多种重质润滑剂基础原料、重质白油、药用油、医用制剂载体或底物中,及作为化学和药物制造方法中成分的用途。
17.如权利要求1所述的组合物,用于降低重质润滑剂基础原料的倾点和浊点中的用途。
18.一种包含如权利要求1所述组合物的重质润滑剂基础原料。
19.一种包括如权利要求18所述重质润滑剂基础原料和一种或多种润滑剂添加剂的重质润滑剂。
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2002
- 2002-10-08 US US10/266,344 patent/US6846778B2/en not_active Expired - Lifetime
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2003
- 2003-08-29 US US10/652,389 patent/US7241375B2/en active Active
- 2003-09-30 TW TW092127065A patent/TW200413519A/zh unknown
- 2003-09-30 AR ARP030103562A patent/AR041442A1/es unknown
- 2003-10-06 MY MYPI20033803A patent/MY127782A/en unknown
- 2003-10-07 CN CNB2003801011709A patent/CN100510032C/zh not_active Expired - Fee Related
-
2005
- 2005-03-29 ZA ZA200502513A patent/ZA200502513B/en unknown
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Also Published As
Publication number | Publication date |
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ZA200502513B (en) | 2006-02-22 |
MY127782A (en) | 2006-12-29 |
CN1703499A (zh) | 2005-11-30 |
TW200413519A (en) | 2004-08-01 |
AR041442A1 (es) | 2005-05-18 |
US20050150815A1 (en) | 2005-07-14 |
US6846778B2 (en) | 2005-01-25 |
US20040067856A1 (en) | 2004-04-08 |
US7241375B2 (en) | 2007-07-10 |
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