CN105593350A - 费托衍生的气油馏分 - Google Patents

费托衍生的气油馏分 Download PDF

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CN105593350A
CN105593350A CN201480053344.7A CN201480053344A CN105593350A CN 105593350 A CN105593350 A CN 105593350A CN 201480053344 A CN201480053344 A CN 201480053344A CN 105593350 A CN105593350 A CN 105593350A
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fischer
tropsch derived
oil
derived gas
boiling point
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R·J·维斯玛
J·图夫博尔
R·雷梅斯玛
J·B·W·莫辛克
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Shell Internationale Research Maatschappij BV
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Abstract

本发明提供了初沸点为至少270℃且终沸点为最高305℃的费托衍生的气油馏分。在另一方面，本发明提供了包含初沸点为至少270℃且终沸点为最高305℃的费托衍生的气油馏分的功能流体制品。

Description

费托衍生的气油馏分
本发明涉及分馏的费托(Fischer-Tropsch)衍生的气油，以及包含其的功能流体制品。
可通过各种方法获得费托衍生的气油馏分。使用所谓的费托法获得费托衍生的气油馏分。这样的方法的实例公开在WO02/070628中。
现在令人惊讶地发现，特定的费托衍生的气油馏分可有利地用于溶剂和功能流体应用中。
为了此目的，本发明提供了初沸点为至少270℃且终沸点为最高305℃的费托气油。
本发明的优点在于费托衍生的气油馏分具有令人惊讶的低粘度、低倾点同时具有高闪点，这些性质的组合在要求低粘度的溶剂和功能流体应用中提供了优点。
典型地，根据本发明的费托衍生的气油馏分具有非常低水平的芳族化合物、环烷烃和杂质。
使用费托衍生的气油馏分因此在溶剂和/或功能流体应用中改善了可生物降解性以及提供了较低的毒性。
根据本发明的费托衍生的气油源自费托法。费托衍生的气油在现有技术中是已知的。术语“费托衍生的”表示气油是或来源于费托法的合成产物。在费托法中，合成气转化成合成产物。合成气体或合成气是通过含烃原料转化而获得的氢气和一氧化碳的混合物。合适的原料包括天然气、原油、重油馏分、煤、生物质和木质素。费托衍生的气油也可以称作GTL(气制液(Gas-to-Liquids))气油。
费托衍生的气油主要是异链烷烃。优选地，费托衍生的气油包含超过75重量％、优选超过80重量％、更优选超过85重量％的异链烷烃。
费托气油的馏分是费托气油的沸程较窄的馏分，并还可以看作是从费托气油蒸馏的GTL衍生的溶剂。根据本发明，费托衍生的气油馏分在大气条件下具有至少270℃的初沸点和最高305℃的终沸点。合适地，费托衍生的气油在大气条件下具有至少274℃的初沸点。进一步地，费托衍生的气油馏分优选具有至少272℃的初沸点。
费托衍生的气油馏分在大气条件下优选具有最高303℃的终沸点。进一步地，费托衍生的气油馏分在大气条件下优选具有至少301℃的终沸点。
大气条件下的沸点表示大气沸点，该沸点通过ASTMD86测定。
优选地，费托衍生的气油馏分的T10体积％沸点为270-288℃、更优选273-285℃、最优选296-282℃，且T90体积％沸点为282-300℃、优选285-297℃且更优选288-294℃。
T10体积％是对应于其中产物的10体积的累积量被回收的大气沸点的温度。类似地，T90体积％是对应于其中产物的90体积％的累积量被回收的大气沸点的温度。可使用大气蒸馏法ASTMD86来确定回收水平，或者气相色谱法例如ASTMD2887，其已被校正来传递类似的结果。
费托衍生的气油馏分优选地包含具有13-19个碳原子的链烷烃；费托衍生的链烷烃气油馏分优选包含至少70重量％、更优选至少85重量％、更优选至少90重量％、更优选至少95重量％、且最优选至少98重量％的具有13-19个碳原子的费托衍生的链烷烃，其基于费托衍生的链烷烃的总量，优选地基于具有12-20个碳原子的费托衍生的链烷烃的量。
进一步地，费托衍生的气油馏分优选地具有根据ASTMD4052、在15℃下，从782kg/m3至788kg/m3、更优选从783kg/m3至787kg/m3、且最优选从784kg/m3至786kg/m3的密度。
合适地，根据ASTMD445的在25℃下的运动粘度为4.4-5.0cSt、优选4.5-4.9cSt、且更优选4.6-4.8cSt。
优选地，费托衍生的气油馏分具有根据ASTMD93的125-135℃、更优选127-133℃且最优选129-131℃的闪点。
费托衍生的气油馏分具有根据ASTMD1322的超过50mm的发烟点。
典型地，根据本发明的费托气油馏分包含小于500ppm芳族化合物、优选小于200ppm的芳族化合物、小于3ppm的硫、优选小于1ppm的硫、更优选小于0.2ppm的硫、小于1ppm的氮且小于4重量％、优选小于3重量％且更优选小于2重量％的环烷烃。
进一步地，费托衍生的气油馏分优选包含小于0.1重量％的多环芳烃、更优选小于25ppm的多环芳烃且最优选小于1ppm的多环芳烃。
异链烷烃的量合适地超过75重量％，优选超过80重量％，基于具有13-19个碳原子的链烷烃的总量。
进一步地，费托衍生的气油馏分可包含正链烷烃和环烷烃。
具有至少270℃的初沸点且最高305℃的终沸点的费托衍生的气油馏分的制备已描述在例如WO02/070628中。
在进一步的方面，本发明提供了功能流体制品，其包含根据本发明的费托衍生的气油馏分，进一步包含添加剂化合物。典型地，功能流体制品可用于许多领域，例如油气开发和生产、建筑业、食品和相关行业、纸、织物和皮革以及各种家用和消费产品。此外，用于根据本发明的功能流体制品中的添加剂的种类取决于流体制品的类型。用于功能流体制品的添加剂包括但不限于腐蚀和流变控制产品、乳化剂和湿润剂、钻孔稳定剂、高压和抗磨损添加剂、消泡沫剂和抗泡沫剂、倾点下降剂和抗氧化剂。
在功能流体制品中使用费托衍生的气油馏分的优点在于费托衍生的气油馏分具有低粘度、低倾点同时具有高闪点。优选地，费托衍生的气油馏分的物理特征的这种组合对于其用于要求低粘度的功能流体制品是高度期望的。
例如，在钻探流体应用中，在使用期间，钻探流体的温度可能降低，其可能导致钻探流体的粘度的提高。高的粘度对于钻探流体的有益用途可能是有害的。因此，根据本发明的具有低粘度和高闪点的费托衍生的气油馏分对于其用于钻探流体应用是高度期望的。
在另一方面，本发明提供了根据本发明的费托衍生的气油馏分作为用于溶剂和/或功能流体应用的稀释油或基础油的用途。
术语稀释油的意思是用于降低溶剂和功能流体制品的粘度和/或改善其其它性质的油。
术语基础油的意思是向其中添加其它油、溶剂或物质以产生溶剂或功能流体制品的油。
使用费托衍生的气油馏分作为用于溶剂和/或功能流体制品的稀释油或基础油的优点与如上对于包含根据本发明的费托衍生的气油馏分、还包含添加剂化合物的功能流体制品所述的相同。
使用根据本发明的费托气油馏分作为稀释油或基础油的优选的溶剂和/或功能流体应用包括但不限于钻探流体、压裂流体、加热燃料、灯油、烧烤点火机、混凝土脱模、杀虫剂喷雾油、水处理、清洁剂、抛光剂、车脱蜡剂、放电加工、变压器油、硅氧烷胶粘剂、二冲程发动机循环油、金属清洁、干洗、润滑剂、金属工作流体、铝辊油、成型油***(formingoilsexplosive)、氯化链烷烃、热定型印刷油墨、木料处理、聚合物加工油、化妆品和个人护理、防锈剂和燃料添加剂制品、油漆和涂料、粘合剂、密封剂和空气清新剂。
通常的溶剂和功能流体应用例如描述在“TheIndexofSolvents”，MichaelAsh,IreneAsh,GowerpublishingLtd,1996,ISBN0-566-07884-8和“HandbookofSolvents”,GeorgeWypych,WillemAndrewpublishing,2001,ISBN0-8155-1458-1中。在进一步的方面，本发明提供了根据本发明的费托衍生的气油馏分用于在溶剂和/或功能流体应用中改善可生物降解性以及降低毒性的用途。
如上所述，费托衍生的气油优选地具有非常低水平的芳族化合物、硫、氮化合物并优选不具有多环芳烃。这些低水平可导致、但不限于所述费托衍生的气油的低的水生生物毒性、低的沉积物有机体毒性和低的陆生生物毒性。根据本发明的费托衍生的气油的分子结构可导致费托衍生的气油馏分容易生物降解。
本发明参考下面的实施例描述如下，所述实施例不旨在以任何方式限制本发明的范围。
实施例
实施例1
具有至少270℃的初沸点和最高305℃的终沸点的费托衍生的气 油的制备
费托产物以类似于WO-A-9934917的实施例III所述的方法，使用WO-A-9934917的实施例III的催化剂进行制备。由此获得的产物的C5+馏分(在环境条件下为液体)被连续进料到加氢裂化步骤(步骤(a))。C5+馏分包含约60重量％的C30+产物。C60+/C30+的比率为约0.55。在加氢裂化步骤中，馏分与EP-A-532118的实施例1的加氢裂化催化剂接触。步骤(a)的流出物在真空下连续蒸馏以得到轻产物、燃料和残余物“R”，其沸点为370℃和更高。沸点高于370℃的产物转化为沸点低于370℃的产物为45-55重量％。将残余物“R”再循环至步骤(a)。加氢裂化步骤(a)的条件为：新鲜进料重时空速(WHSV)为0.8kg/l.h、再循环进料WHSV为0.4kg/l.h、氢气速率＝1000Nl/kg、总压＝40巴、反应器温度在330-340℃范围内。
获得的燃料馏分(C5+，370℃)在表1中给出的条件下连续蒸馏以得到作为塔底产物的气油馏分。表1和2中给出物理性质。
表1
表2
表3
实施例2
使用费托衍生的气油作为用于溶剂和/或功能流体应用的稀释油/ 基础油。
表1-3中给出的费托衍生的气油的性质是费托衍生的气油在以下应用中有利地使用的关键性质：钻探流体、压裂流体、加热燃料、灯油、烧烤点火机、混凝土脱模、杀虫剂喷雾油、水处理、清洁剂、抛光剂、车脱蜡剂、放电加工、变压器油、硅氧烷胶粘剂、二冲程发动机循环油、金属清洁、干洗、润滑剂、金属工作流体、铝辊油、成型油***(formingoilsexplosive)、化妆品和个人护理、防锈剂、氯化链烷烃、热定型印刷油墨、木料处理、聚合物加工油、和燃料添加剂制品、油漆和涂料、粘合剂、密封剂和空气清新剂。
实施例3
在表4中，根据本发明的费托衍生的气油的性质与IsoparTMV*的性质进行比较。
表4
*IsoparTMV的数据获自2010年10月发行的ImperialoilProductsandChemicalsDivision出版的手册。
讨论
表1-3的结果表明获得了具有低粘度和高闪点的费托衍生的气油馏分。
表4的结果表明在可比的初沸点和闪点下，费托衍生的气油馏分具有比IsoparTMV更低的运动粘度。
这表明，费托衍生的气油馏分对于其用于要求低粘度的溶剂和功能流体制品，与在相同制品中使用IsoparTMV相比，是更期望的。

Claims (11)

1.具有至少270℃的初沸点和最高305℃的终沸点的费托衍生的气油馏分。
2.根据权利要求1所述的费托衍生的气油馏分，其具有至少274℃的初沸点。
3.根据权利要求1或2所述的费托衍生的气油馏分，其具有至少301℃且最高303℃的终沸点。
4.根据权利要求1至3任一项所述的费托衍生的气油馏分，其具有270-288℃、优选273-285℃、更优选296-282℃的10体积％沸点，和282-300℃、优选285-297℃且更优选288-294℃的T90体积％沸点。
5.根据权利要求1至4任一项所述的费托衍生的气油馏分，其具有根据ASTMD4052的在15℃下782-788kg/m3、优选783-787kg/m3、更优选784-786kg/m3的密度。
6.根据权利要求1至5任一项所述的费托衍生的气油馏分，其具有根据ASTMD445的在25℃下4.4-5.0cSt、优选4.5-4.9cSt、且更优选4.6-4.8cSt的运动粘度。
7.根据权利要求1至6任一项所述的费托衍生的气油馏分，其具有根据ASTMD93的125-135℃、优选127-133℃且更优选129-131℃的闪点。
8.根据权利要求1至7任一项所述的费托衍生的气油馏分，其具有根据ASTMD1322的超过50mm的发烟点。
9.包含根据权利要求1-8任一项所述的费托衍生的气油馏分的功能流体制品，其进一步包含添加剂化合物。
10.根据前述权利要求1-9的一项或多项所限定的费托衍生的气油馏分作为用于溶剂和/或功能流体制品的稀释油或基础油的用途。
11.根据前述权利要求1-10的一项或多项所限定的费托衍生的气油馏分用于在溶剂和/或功能流体应用中改善可生物降解性以及降低毒性的用途。
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