CN1081667C - 合成柴油及其生产方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- Chemical Kinetics & Catalysis (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
通过把费-托蜡分离成为较重的馏分和较轻的馏分，进一步把该较轻的馏分分离，并且较重的馏分和低于约500的较轻的馏分进行加氢异构化，由此来从费-托蜡生产用作柴油或柴油调合料的洁净的馏分油。把该异构的产物与未加氢处理的部分较轻的馏分调合。
Description
发明领域
本发明涉及一种馏分物料，该馏分物料具有高十六烷值并且可以作为柴油或者作为其调合料，并涉及该馏分物料的制备方法。更具体地说，本发明涉及由费-托合成蜡生产馏分物料的方法。
发明背景
不含有即没有硫、氮或芳烃的洁净馏分作为柴油或调合柴油是或者可能是非常需要的。具有比较高的十六烷值的洁净馏分是特别有价值的。一般的石油衍生的馏分是不洁净的，一般的它们含有显著量的硫、氮和芳烃，并且它们的十六烷值比较低。通过高费用的苛刻的加氢处理可以从石油基馏分生产洁净馏分。这样的苛刻的加氢处理对十六烷值的改善很小，对燃料的润滑性能也是不利的。可以通过使用比较贵的添加剂整套配方来改善燃料输送系统的有效操作所需要的燃料润滑性能。在公开的文献中已经讨论了由费-托合成蜡生产洁净的高十六烷值的馏分的方法，但是所公开的生产这样的馏分的方法也使得该馏分缺少一种或多种重要的性能，例如润滑性能。因此，所公开的费-托合成馏分需要与其它的不合乎要求的原料调合或者使用很贵的添加剂。这些较早的方案公开了加氢处理全部的费-托合成产物，包括完全的700°F-馏分。该加氢处理使得从该馏分中脱除了氧化物质。
根据本发明，保留了少量的氧化物质，所得到的产物具有很高的十六烷值和很高的润滑性能。因此该产物本身就可以作为柴油，或者作为由其它的较低级的物料来制备柴油的调合料。
发明概述
根据本发明，优选的可以由费-托合成蜡，优选的由钴或钌催化剂所得到的费-托合成蜡，通过把该含蜡的产物分离成为较重的馏分和较轻的馏分来生产洁净的馏分，该馏分可以用作柴油或者作为柴油的调合料，该洁净的馏分的十六烷值至少约60，优选至少约70，更优选至少约74。该标称的分离在约700°F进行，该较重的馏分主要含有700°F+的馏分，该较轻的馏分主要含有700°F-的馏分。
通过进一步地分离该700°F-的馏分为至少两种其它的馏分：(i)含有伯C12+醇的一种和(ii)不含这样的醇的一种。该馏分(ii)优选是500°F-的馏分，更优选是600°F-的馏分，还更优选是C5-500°F的馏分，或C5-600°F的馏分。把馏分(i)和该较重的馏分在加氢异构化催化剂存在下和在加氢异构化条件下进行加氢异构化。这些馏分的加氢异构化可以分别进行或在同样的反应区，优选在同样的反应区进行。在任何情况下，至少一部分700°F+的物料转化成为700°F-的物料。然后，至少一部分，优选所有的加氢异构化的700°F-的物料与至少一部分，优选所有的馏分(ii)混合，该馏分(ii)优选地是500-700°F的馏分，更优选地是600-700°F的馏分，还更优选的特征是不存在任何的加氢处理，例如加氢异构化。由该混合的产物可以回收沸点范围为250°F-700°F的柴油或柴油调合料，该柴油或柴油调合料具有下面所述的性质。
附图的说明
图1是本发明的方法的流程图。
图2是250°F-500°F的馏分(上面的曲线)和500°F-700°F的馏分(下面的曲线)的过氧化物数(纵坐标)和试验时间(天)(横坐标)的关系图。
优选实施方案的描述
参考附图来更详细地描述本发明。在管线1中所含有的合成气、氢气和一氧化碳按照合适的比例加入到费-托合成反应器2中，优选的是浆液反应器，从管线3和4分别回收700°F+和700°F-的产物。该较轻的馏分通过热分离器6，在管线8中回收500-700°F的馏分，而在管线7中回收500°F-的馏分。该500°F-的馏分通过冷却分离器9，由其在管线10中回收C4-气体。在管线11中回收C5-500°F的馏分，并且与管线3中的700°F+的馏分混合。至少一部分，优选几乎全部，更优选基本上所有的该500°F-700°F的馏分与管线12中的加氢异构化的产物调合。
把在管线3中的较重的，例如700°F+的馏分与管线11中的较轻的馏分例如C5-500°F的馏分一起送到加氢异构化装置5中。下面的表中列出了加氢异构化过程装置的反应器的一般的操作条件。
加氢异构化方法是公知的，下面的表中列出的是该步骤的某些宽的和优选的条件。
条件 宽范围 优选范围温度°F 300-800 550-750总压力，psig 0-2500 300-1200氢处理速率，SCF/B 500-5000 2000-4000氢耗速率，SCF/B 50-500 100-300
虽然实际上用于加氢异构化或选择性加氢裂化的任何的催化剂都可以满足该步骤，但是某些催化剂比其它催化剂好并且是优选的。例如，含有担载VIII族贵金属例如铂或钯的催化剂是有用的，含有一种或多种VIII族基本金属例如镍、钴的含量约为0.5-20％(重)的催化剂也是有用的，其可以或也可不包括量约为1.0-20％(重)的VI族金属例如钼。这些金属的载体可以是任何的难熔的氧化物或沸石或其混合物。优选的载体包括氧化硅、氧化铝、氧化硅-氧化铝、氧化硅-氧化铝磷酸盐、氧化钛、氧化锆、氧化钒和其它III族、IV族、VA族和VI族氧化物，以及Y型分子筛例如超稳Y分子筛。优选的载体包括氧化铝和氧化硅-氧化铝，其中主体载体中的氧化硅的浓度小于约50％(重)，优选小于35％(重)。
优选的催化剂的表面积是约200-500m2/gm，孔体积优选为0.35-0.80ml/gm，其是水脱附测定的，堆积密度约为0.5-1.0g/ml。
该催化剂含有VIII族非贵金属例如铁、镍，连同IB族金属例如铜，担载在酸性载体上。该载体优选是无定型氧化硅-氧化铝，其中氧化铝的存在量小于约30％(重)，优选5-30％(重)，更优选10-20％(重)。另外，该载体可以含有少量的例如20-30％(重)的粘合剂，例如氧化铝、氧化硅、IVA族金属氧化物和各种类型的粘土，氧化镁等，优选氧化铝。
在Ryland，Lloyd B.，Tamele，M.W.，and Wilson，J.N.，Cracking Catalysts，Catalysis：VolumeVII，Ed.Paul H.Emmertt，Reinhold Publishing Corporation，New York，1960，pp.5-9中介绍了无定型氧化硅-氧化铝微球的制备方法。
把金属从溶液中共浸到载体上，在100-150℃干燥，在200-550℃空气中焙烧，来制备该催化剂。
VIII族金属的存在量约为15％(重)或更少，优选1-12％(重)，而IB族金属通常的存在量比较少，例如其与VIII族金属的比为1∶2-约1∶20。典型的催化剂表示如下：
Ni，％(重) 2.5-3.5
Cu，％(重) 0.25-0.35
Al2O3-SiO2 65-75
Al2O3(粘合剂) 25-30
表面积 290-355 m2/gm
孔体积(Hg) 0.35-0.45ml/gm
堆积密度 0.58-0.68g/ml
在加氢异构化装置中，700°F+的物料转化为700°F-的物料约为20-80％，优选20-50％，更优选约30-50％。在加氢异构化的过程中基本上所有的烯烃和含氧的物质都被加氢。
在管线12中回收的加氢异构化的产物进到管线8中的500°F-700°F的物流中进行调合。在塔13中分馏该调合的物流，由其，在管线14中的700°F+的馏分任意地循回到管线3中，在管线16中回收C5-的馏分，其可以与在管线10中由冷分离器9得到的轻气体混合形成物流17。在管线15中回收沸点范围为250-700°F的洁净馏分油。该馏分油有极好的性能，可以用作柴油或者用作柴油的调合组分。
把该C5-500°F的馏分通过加氢异构化装置具有进一步减少产物物流12和15中的烯烃浓度的作用，由此，进一步改善产物的氧化稳定性。在产物中的烯烃的浓度少于0.5％(重)，优选少于0.1％(重)。因此，该烯烃的浓度足够地低，以至于使得没有必要回收烯烃，并且避免为烯烃而要进一步处理该馏分。
把700°F-物流分离成为C5-500°F物流和500-700°F物流，如上所述，C5-500°F物流加氢异构化，以降低产物中的烯烃的浓度。然而，另外，C5-500°F物流中的含氧的化合物具有减少加氢异构化的甲烷产率的作用。理想的是，加氢异构化反应包括很少的或没有费-托蜡的裂解。不会经常达到理想的条件，总是伴随着该反应产生一定的裂化，生成气体，特别是甲烷。关于此处所公开的加工方案，该700°F+馏分和C5-500°F馏分的加氢异构化使得甲烷的产率减少至少50％，优选至少75％。
从分馏塔回收的柴油物料有下表所示的性质：
烷烃 至少95％(重)，优选至少96％(重)，更优选至少
97％(重)，仍然更
优选至少98％(重)，最优选至少99％(重)；异构/正构比 约0.3-3.0，优选0.7-2.0；
硫 ≤50ppm(重)，优选没有；
氮 ≤50ppm(重)，优选≤20ppm(重)，更优选没有；
不饱和物 ≤0.5％(重)，优选≤0.1％(重)；
(烯烃和芳烃)
氧化物质 约0.001到少于0.3％(重)的氧(无水基)
异构烷烃通常是单甲基支链的，因为该方法使用费-托蜡，所以该产物不含有环状烷烃，例如没有环己烷。
在较轻的馏分例如700°F-的馏分中，所含的氧化产品基本上是例如≥95％的氧化合物。
优选的费-托合成方法是这样一种方法：使用非变换(即没有水气转换能力)催化剂，例如钴或钌或其混合物，优选钴，并且优选的是助催化的钴，该助催化剂是锆或铼，优选铼。这样的催化剂是公知的，在U.S.P4,568,663和EP0266898中介绍了优选的催化剂。
费-托合成方法的产物主要是烷烃。钌主要生产馏分油沸点范围例如C10-C20的烷烃；而钴催化剂一般地生产更多的较重的烃例如C20+，钴是优选的费-托合成催化金属。
好的柴油一般的具有如下性质：高的十六烷值，通常50或更高，优选至少约60，更优选至少约65，或更好的润滑性，氧化稳定性和与柴油管道规格相容的物理性能。
本发明的产品本身就可以用作柴油，或用来与其它的不合乎要求的含有大约相同的沸点范围的原料的石油或烃调合。当用作调合料时，可以使用比较少量的本发明的产品，例如10％或多点，就可以明显的改善最终调合柴油产品。虽然本发明的产品会改善几乎任何的柴油产品，但是特别合乎要求的是把该产品与低质量的炼厂柴油物料调合。一般的物流是粗的或加氢催化的或热裂化的馏分油和瓦斯油。
通过使用费-托合成方法，回收的馏分油基本上没有硫和氮。这些杂原子化合物对费-托合成催化剂是有毒的，它们要从含甲烷的天然气中除去，天然气是费-托合成方法的便宜的原料。(在任何情况下，在天然气中，含硫和氮的化合物都是非常低浓度的)。另外，该方法不产生芳烃，或者在通常的操作条件下实际上不产生芳烃。因为所提供的生产烷烃的通道通过烯烃中间产物，所以产生一定量的烯烃。虽然，烯烃的浓度通常非常的低。
含氧化合物包括在费-托合成过程中产生的醇和某些酸，但是在至少一种公知的方法中，含氧化合物和不饱和化合物通过加氢处理都完全从产物中消除了。例如见The Shell Middle Distillate Process，Eiler，J.，Posthuma，S.A.；Sie，S.T.，Catalysis Letter，1990，7，253-270。
但是，我们已经发现，在500-700°F的馏分中，通常以浓缩形式的少量的氧化合物，优选醇，对柴油提供所希望的润滑性。例如，按所具体说明的那样将表明，含有少量的氧化合物的高含量烷烃的柴油，由BOCLE试验(球在汽缸润滑性能评价装置上)所表示的那样，具有优异的润滑性能。但是，当例如通过萃取、分子筛吸附、氢加工等除去氧化合物，使得在试验的馏分中氧的含量小于10ppm％(重)(无水基)时，润滑性能就非常差。
根据于本发明所公开的加工方法，较轻的700°F-的馏分，即500-700°F的馏分不进行任何的加氢处理。在该馏分不进行加氢处理的情况下，在该馏分中的少量的氧化合物，主要是直链醇被保存，而在加氢异构化步骤中在较重的馏分中的氧化合物被除去。在加氢异构化的过程中，在C5-700°F的馏分中所含的某些氧化合物将转化为烷烃。但是，为了润滑的目的，有价值的含氧化合物，最优选C12-C18伯醇是在未处理的500-700°F的馏分中。加氢异构化也增加在馏分燃料中的异构烷烃的量，并使得该燃料满足倾点和浊点的规格，为了这些目的虽然可以使用添加剂。
被认为是提高润滑性能的氧化合物可以描述为其具有的氢键合能大于烃的键合能(各种化合物的能量测定可以从标准参考书中获得)；该差别越大，润滑效果越好。氧化合物也具有亲油端和亲水端，以使燃料润湿。
优选的氧化合物，主要是醇，具有比较长的链，即C12+，更优选C12-C24直链伯醇。
当酸是含氧化合物时，在费-托合成的过程中，在非变换的条件下，会产生很少量的酸，酸是腐蚀性的。与由直链醇所表示的优选的一氧化合物相对比，这些酸也是二氧化合物。因此，二或多氧化合物通常用红外测量是不可检测的，例如按氧计是小于约15wppm氧。
本领域的技术人员都熟知非变换费-托合成反应，其特征是其条件使得形成的CO2副产物减少到最少。通过各种各样的方法，包括一种或多种下面的方法可以达到这些条件：在低的CO分压下操作，即在氢与CO的比至少约1.7/1，优选约1.7/1-2.5/1，更优选至少约1.9/1，并且在1.9/1-2.5/1的范围内操作，所有的都具有至少约0.88的α，优选至少约0.91；温度约175-225℃，优选180-210℃；使用含有钴或铼的催化剂作为主要费-托合成催化剂。
以无水基的氧计，要达到所要求的润滑性能，存在的氧化合物的量是较少的，即至少约0.001％(重)的氧(无水基)，优选0.001-0.3％(重)的氧(无水基)，更优选0.0025-0.3％(重)的氧(无水基)。
下面的实施例将用来说明本发明，但不是限制本发明。
在浆液费-托合成反应器中，氢和一氧化碳合成气(H2∶CO 2.11-2.16)转化成重的烷烃。费-托合成反应所用的催化剂是在前面的USP4,568,663中所描述的氧化钛载钴/铼催化剂。反应条件是422-428°F，287-289psig，线速度是12-17.5厘米/秒。最初的费-托合成步骤的α是0.92。然后，以三种不同标称沸点的物流分离烷烃费-托合成产物，使用粗略的闪蒸来分离。这三种沸点接近的馏分_：1)C5-500°F的馏分，下面称为F-T冷分离器液体；2)500-700°F的馏分，下面称为F-T热分离器液体；和3)700+°F的馏分，下面称为F-T反应器蜡。
实施例1
把70％(重)的加氢异构化的F-T反应器蜡、16.8％(重)的加氢处理的F-T冷分离器液体和13.2％(重)的加氢处理的F-T热分离器液体混合在一起，并很好的混合。柴油A是通过蒸馏分离出的该调和物的260-700°F的馏分，其按如下制备：按USP5,292,989和USP5,378,348所述，使用含有钴和钼促进的无定型氧化硅-氧化铝催化剂的固定床装置，一次通过，来制备该加氢异构化的F-T反应器蜡。加氢异构化的条件是708°F，750psig H2，2500SCF/B H2，液时空速(LHSV)是0.7-0.8。使用循环的未反应的700°F+的反应器蜡进行加氢异构化。混合的进料比(新鲜进料+循环进料)/新鲜进料等于1.5。使用一次通过的固定床反应器和市场上买到的镍催化剂，制备加氢处理的F-T冷分离器液体和F-T热分离器液体。加氢处理的条件是450°F，430 psig H2，1000 SCF/B H2，和3.0LHSV。燃料A是一般的完全加氢处理的钴衍生的费-托柴油的代表，其是本领域公知的。
实施例2
把78％(重)的加氢异构化的F-T反应器蜡、12％(重)的未加氢处理的F-T冷分离器液体和10％(重)的F-T热分离器液体混合在一起，并很好的混合。柴油B是通过蒸馏分离出的该调和物的250-700°F的馏分，其按如下制备：按USP5,292,989和USP5,378,348所述，使用含有钴和钼促进的无定型氧化硅-氧化铝催化剂的固定床装置，一次通过，来制备该加氢异构化的F-T反应器蜡。加氢异构化的条件是690°F，725psigH2，2500SCF/B H2，液时空速(LHSV)是0.6-0.7。燃料B是本发明的
实施例的代表。
实施例3
通过蒸馏燃料B成为两个馏分来制备柴油C和D。柴油C代表柴油B的250-500°F的馏分，柴油D代表柴油B的500-700°F的馏分。
实施例4
100.81克柴油B与33.11克适度硅铝酸盐沸石：13X，等级544，812目颗粒接触，柴油E是由该处理得到的滤液。该处理有效地从燃料中除去了醇和其它氧化合物。
实施例5
使用质子核磁共振(1H NMR)、红外光谱(IR)和气相色谱/质谱(GC/MS)来测定柴油A、B和E的氧化合物、二氧化合物和醇组成。使用BruckerMSL-500谱仪进行1H NMR试验。使用频率500.13Mhz，脉冲宽度2.9μs(45度斜角)，延迟60s，和64扫描，在常温下测定溶解在CDCl3中的样品，得到定量数据。在每一种情况下，都使用四甲基硅烷作为内参，二噁烷作为内标。通过与内标比较分别在3.6(2H)、3.4(1H)、4.1(2H)和2.4(2H)的整体峰，来直接估算伯醇、仲醇、酯和酸的量ppm。使用Nicolet800光谱仪进行IR光谱分析。把样品放在KBr固定的光程长度盒(额定1.0mm)来制备样品，并且加4096扫描0.3cm-1分辨来进行测量。分别用在1720和1738cm-1的吸光度来测定二氧化合物例如羧酸和酯的量。使用Hewlett-Packard 5980/Hewlett-Packard 5970B Mass Selective DetecterCombination(MSD)或者Kratos Modle MS-890 GC/MS来进行GC/MS。使用选择的离子检测m/z31(CH3O+)来定量伯醇。把称量的C2-C14、C16和C18伯醇加入到C8-C16正构烷烃的混合物中来制备外标。按ASTM D 2710所述，用溴指数来确定烯烃。这些分析的结果列于表1。含有未加氢处理的热和冷分离器液体的柴油B含有明显量的氧化合物例如直链伯醇。这些重要的馏分是重要的C12-C18伯醇。提供柴油的优异的润滑性能的是这些醇。在基本上除去所有量的氧化合物和烯烃方面加氢处理(柴油A)是极为有效的。在除去醇污染物方面，不使用过程氢的分子筛处理(柴油E)也是有效的。这些燃料中没有含有明显量的二氧化合物例如羧酸或酯的。
表1
所有的加氢处理的柴油(柴油A)、部分加氢处理的柴油(柴油B)和分子筛处理的部分加氢处理的柴油(柴油E)的氧化合物和二氧化合物(羧酸，酯)组成。
柴油A 柴油B 柴油E二氧化合物(羧酸，酯) 未检测 未检测 未检测中的wppm氧-(IR)C5-C18伯醇中的 未检测 640ppm 未检测wppm氧-(1H NMR)C5-C18伯醇中的 5.3 824ppm 未检测wppm氧-(GC/MS)C12-C18伯醇中的 3.3 195ppm 未检测wppm氧-(GC/MS)总烯烃-摩尔/克(溴指数， 0.004 0.78 -ASTM D 2710)
实施例6
也按Lacey，P.I.“The U.S.Army Scuffing Load Wear Test”，1994年1月1日所述，使用标准的球关于汽缸润滑性能评价(BOCLE)对柴油A-E都进行试验。该试验是基于ASTM D 5001。结果列于表2，其是作为在Lacey中所述的参照燃料2的百分比。
表2
燃料A-E的BOCLE结果，结果是在Lacey中所述的参照燃料2的百分比。
柴油 参照燃料2％
A 42.1
B 88.9
C 44.7
D 94..7
E 30.6
完全加氢处理的柴油A呈现出非常低的完全是烷烃柴油的一般的润滑性能。柴油B含有大量的氧化合物如直链C5-C24伯醇，柴油B呈现出非常优异的润滑性能。柴油E是通过13X分子筛脱附从柴油B分离出氧化合物制备的。柴油E呈现出非常差的润滑性能，表明柴油B的高润滑性能是由直链C5-C24伯醇带来的。柴油C和D分别表示柴油B的250-500°F和500-700°F沸点的馏分。柴油C含有沸点低于500°F的直链C5-C11伯醇，柴油D含有沸点为500-700°F的直链C12-C24伯醇。与柴油C比较，柴油D呈现出非常优异的润滑性能，实际上，柴油D性能优于获得其的柴油B。这就清楚的表明，要生产高润滑性能的饱和燃料，沸点为500-700°F的直链C12-C24伯醇是很重要的。柴油B比柴油D呈现出较差的润滑性能的这种事实也表明在柴油B的250-500°F馏分中所含的轻的氧化合物不利地限制了提供在500-700°F的柴油B中所含的C12-C24伯醇的优点。因此，生产含有最少量的不合乎要求的C5-C11轻伯醇，而含有最大量的有利的C12-C24伯醇的柴油是所要求的。这可以通过选择性的加氢处理250-500°F沸点的冷分离器液体而不是选择性的加氢处理500-700°F沸点的热分离器液体来完成。
实施例7
通过观察一定的时间后过氧化氢的出现情况来试验柴油C和D的氧化稳定性。柴油C和D分别代表柴油B的250-500°F和500-700°F沸点的馏分。该试验完全按ASTM D3703所述进行。更稳定的燃料将呈现出滴定的过氧化氢数的增加速度较慢。通过在开始和在试验过程中的定期的间隔进行碘滴定来测定过氧化物的量。由于这些燃料的固有的稳定性，所以它们在开始出现过氧化物之前都首先在25℃(室温)老化7周的时间。图2表示柴油C和D经过一定的时间出现过氧化物的情况。可以清楚的看出，250-500°F沸点的柴油C比500-700°F沸点的柴油D稳定性差。柴油C的相对的不稳定性是由于它含有大于90％的在柴油B中所发现的烯烃所造成的。本领域都熟知烯烃导致氧化不稳定性。这些相对不稳定的轻烯烃的饱和是250-500°F冷分离器液体加氢处理的另一个原因。
Claims (14)
1.一种可用作比汽油重的燃料或用作馏分燃料的调合组分的物料，其包括由费-托催化方法所得到的250-700°F的馏分，该馏分含有至少95％(重)的异构与正构比为0.3-3.0的烷烃、硫和氮均≤50ppm(重)、少于0.5％(重)的不饱和烃和0.001-少于0.3％(重)的氧，无水基。
2.权利要求1的物料，其中氧主要是作为直链醇存在。
3.权利要求2的物料，其中直链醇是C12+的醇。
4.权利要求3的物料，其特征在于十六烷值至少70。
5.一种生产比汽油重的馏分燃料的方法，其包括：
(a)把费-托方法的产物分离成为较重的馏分和较轻的馏分；
(b)进一步分离该较轻的馏分成为至少两种馏分：(i)至少一种主要含有C12+醇的馏分和(ii)一种或多种其它馏分；
(c)在加氢异构化的条件下加氢异构化至少一部分步骤(a)的较重的馏分和至少一部分(b)(ii)馏分，并且回收700°F-的馏分；
(d)把至少一部分步骤(b)(i)馏分与至少一部分步骤(c)的700°F-的馏分调合。
6.权利要求5的方法，其中从步骤(d)的调合产物回收沸点范围250-700°F的产物。
7.权利要求6的方法，其中从步骤(d)回收的产物含有0.001-0.3％(重)的氧，无水基。
8.按照权利要求7的方法获得的产物。
9.权利要求6的方法，其中馏分(b)(i)基本上含有所有的C12+伯醇。
10.权利要求6的方法，其中馏分(b)(i)的特征是未加氢处理。
11.权利要求6的方法，其中馏分b)(i)含有C12-C24伯醇。
12.权利要求5的方法，其中费-托方法的特征是非变换条件。
13.权利要求5的方法，其特征在于馏分b)(ii)是500°F-的馏分。
14.权利要求5的方法，其特征在于馏分b)(ii)是600°F-的馏分。
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