CN1082541C - 合成柴油及其生产方法 - Google Patents

合成柴油及其生产方法 Download PDF

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CN1082541C
CN1082541C CN96197172A CN96197172A CN1082541C CN 1082541 C CN1082541 C CN 1082541C CN 96197172 A CN96197172 A CN 96197172A CN 96197172 A CN96197172 A CN 96197172A CN 1082541 C CN1082541 C CN 1082541C
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R·J·维藤布林克
R·F·鲍曼
P·J·伯洛维茨
B·R·库克
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • 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

Abstract

把费-托合成产物分离成为例如小于约371℃和大于约371℃的较轻的和较重的馏分，把371℃+的馏分进行加氢处理，并且把加氢处理的产物的371℃-部分与未加氢处理的较轻的馏分混合，由非变换的费-托法生产具有优异的润滑性、氧化稳定性和高的十六烷值的柴油或调合料。

Description

合成柴油及其生产方法
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现在是或者将来也可能是非常需要的。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371℃-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，优选的由钴或钌费-托合成催化剂所得到的费-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，该馏分可以用作比汽油重的燃料，例如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371℃进行，该较重的馏分主要含有371℃+的馏分，该较轻的馏分主要含有371℃-的馏分。
把该较重的馏分在加氢异构化催化剂存在下，在通常的加氢异构化条件下进行加氢异构化，该加氢异构化催化剂含有一种或多种贵金属或非贵金属，在此当中，至少一部分371℃+的物料转化成为371℃-的馏分。至少一部分，优选所有的较轻的馏分，优选在分离C5-(虽然某些C3和C4可能溶解在C5+中)之后，仍然未被处理，即不被物理分离，并且与至少一部分且优选全部的加氢异构化的371℃-的产物调合。由该混合的产物可以回收沸点范围为121℃-371℃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表示两种燃料的IR吸收度谱图：I柴油B，和II具有0.0005mmol/gm棕榈酸(palnitic acid)(按氧计，其相当于15wppm氧)的柴油B；纵坐标为吸收度，横坐标为波长。
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371℃+和371℃-的产物。较轻的馏分通过热分离器6，在管线8中回收260℃-371℃的馏分，而在管线7中回收260℃-的馏分。该260℃-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C5-371℃的馏分，并且与管线8中的260℃-371℃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C5-371℃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371℃+的馏分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一般较宽的和优选的条件。
        条件                   宽范围              优选范围
温度                           149-427              287-399
总压力，MPa                    0-17.2               2-8.25
氢处理速率，NL/L               89-890               356-712
氢耗速率，NL/L                 8.9-89               17.8-53.4
虽然实际上用于加氢异构化或选择性的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族贱金属例如镍、钴的含量约为0.5-20％(重)的催化剂也是有用的，其可以或也可以不包括量约为1-20％(重)的VI族金属例如钼。这些金属的载体可以是任何的耐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少于约50％(重)，优选少于35％(重)。
优选的催化剂的表面积是约180-400m2/gm，优选230-350m2/gm，孔体积为0.3-1.0ml/gm，优选0.35-0.75ml/gm，堆积密度约为0.5-1.0g/ml，侧向抗碎强度约为0.8-3.5kg/mm。
优选的催化剂含有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。通过把金属从溶液中共沉淀到载体上，在100-150℃干燥，并在200-550℃空气中焙烧来制备该催化剂。
在Ryland，Lloyd B.，Yamele，M.W.，and Wilson，J.N.，Cracking Catalysts，Catalysis：VolumeVII，Ed.Paul H.Emmertt，Reinhold Publishing Corporation，New York，1960，pp.5-9中介绍了用作载体的无定型氧化硅-氧化铝微球的制备方法。
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                                290-355m2/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371℃+的物料转化为371℃-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，管线8和11中的C5-371℃的物流在管线12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371℃+的馏分任意地循回到管线3中，在管线16中回收C5-的馏分，在管线15中回收沸点范围为121-371℃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。可以在管线16中回收轻的气体，并且在管线17中与由冷分离器9分离出的轻的气体混合，用作燃料或化学品的加工过程。
从分馏塔13回收的柴油馏分有下面所示的性质：
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                        ≤2％(重)；
(烯烃和芳烃)
氧化物质                        约0.001到少于0.3％(重)的氧(无水基)
异构烷烃优选是单甲基支链的，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371℃-的馏分中，该氧化产品基本上含有例如之95％的氧化产物。另外，较轻馏分中的烯烃的浓度足够的低，以使得没有必要回收烯烃，并且进一步的避免处理该馏分中的烯烃。
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，优选的催化剂在U.S.P4，568，663和EP0266898中作了介绍。在该方法中，H2∶CO比是至少约1.7，优选至少约1.75，更优选1.75-2.5。
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。
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；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，但是特别希望把该产品与低质量的炼厂柴油物料调合。一般的物料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。不过，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371℃-的馏分中，优选在260-371℃的馏分中，更优选在315-371℃的馏分中的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、加氢等除去氧化合物，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371℃-的馏分不进行任何的加氢处理。在较轻的的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。加氢异构化也为了增加馏分燃料中的异构烷烃的量，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伯直链醇。
虽然酸是含氧化合物，但酸是腐蚀性的，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。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α值至少约0.88，优选至少约0.91；温度约175-225℃，优选180-210℃；使用含有钴或铼作为主要费-托合成催化剂的催化剂。
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∶CO2.11-2.16)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216-220℃，1.97-1.99MPa，线速度是12-17.5厘米/秒。费-托合成步骤的α值是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是：1)C5-260℃的馏分，指定低于F-T冷分离器液体；2)260-371℃的馏分，指定低于F-T热分离器液体；和3)700+℃的馏分，指定低于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合物的126-371℃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375℃，5.15MPa H2，445NL/LH2，液时空速(LHSV)是0.7-0.8。使用循环的未处理的371℃+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232℃，2.95MPaH2，178NL/LH2，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合物的121-371℃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365℃，4.98MPaH2，445NL/LH2，液时空速(LHSV)是0.6-0.7。燃料B是本发明的代表性实施例。
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121-260℃的馏分，柴油D代表柴油B的260-371℃的馏分。
实施例4
100.81克柴油B与33.11克Grace硅铝酸盐沸石：13X，等级544，8-12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氧化合物。
实施例5
柴油F是加氢处理的由大约40％的催化馏分和60％直馏馏分组成的石油物流。其后，其在工业加氢处理装置进行加氢处理。该石油馏分的沸点范围是121-426℃，含有663ppm硫(x-光)和40％FIA芳烃。柴油F代表本发明的石油的基本情况。实施例6
混合等量的柴油B和柴油F来制备柴油G。柴油G应该含有600ppm总氧(中子活化法)，80ppm260℃沸点的伯醇(GC/MS)，伯醇的信号表明320ppm作为伯醇的总氧(1HNMR；121-371℃)。柴油G代表本发明的另一个例子，其中HCS和石油馏分都用于包括柴油。
实施例7
使用质子核磁共振(1HNMR)、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1HNMR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Nicolet 800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内标。按ASTMD2710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。这些主要的馏分是重要的C12-C18伯醇。提供柴油的优异的润滑性能的是这些醇。在除去基本上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。图2表示柴油B的样品的IR谱图。
                          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)中的wppm氧-(IR)   未检测     未检测    未检测C5-C18伯醇中的wppm氧-(1HNMR)        未检测     640ppm    未检测C5-C18伯醇中的wppm氧-(GC/Ms)         5.3       824       未检测C12-C18伯醇中的wppm氧-(GC/MS)        3.3       195ppm    未检测总烯烃-摩尔/克(溴指数，ASTMD2710)      0.004     0.78      -
实施例8
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-G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-G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
                 F                   80.0
                 G                   84.4
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分离氧化合物制备的。柴油E呈现出非常差的润滑性能，表明直链C5-C24伯醇使柴油B具有高润滑性能。柴油C和D分别表示柴油B的121-260℃和260-371℃沸点的馏分。柴油C含有沸点低于260℃的直链C5-C11伯醇，柴油D含有沸点为260-371℃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性能优于柴油B，由柴油B得到柴油D。这就清楚的表明，要生产高润滑性能的饱和柴油，沸点为260-371℃的直链C12-C24伯醇是很重要的。柴油F是由石油得到的低硫柴油的代表，虽然其呈现出相当高的润滑性能，但是没有高链烷烃柴油B的那么高。柴油G是柴油B和柴油F的1∶1的调合物，与柴油F比较，其呈现出改善的润滑性能。这表明高链烷柴油B不仅是很好的洁净的燃料组合物，而且也是能够改善由石油得到的低硫柴油的性能的很好的柴油调合组分。

Claims (11)

1.一种可用作柴油的物料，其包括由非变换费-托催化方法所得到的121-371℃的馏分，所述馏分含有至少95％(重)的异构与正构比0.3-3.0的链烷烃、≤50ppm(重)的硫和氮、少于2％(重)的不饱和烃和0.001-少于0.3％(重)的氧。
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+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，其中较轻馏分含700°F-馏分而较重馏分为含700°F+馏分；
(b)在加氢异构化的条件下加氢异构化该较重的馏分，并且由其回收371℃-的馏分；
(c)把至少一部分步骤(b)回收的馏分与至少一部分较轻的馏分调合。
6.权利要求5的方法，其中从步骤(c)的调合产物回收沸点范围121-371℃的产物。
7.权利要求6的方法，其中从步骤(c)回收的产物含有0.001-0.3％(重)的氧，无水基。
8.权利要求6的方法，其中较轻的馏分的特征是未加氢处理。
9.权利要求6的方法，其中较轻的馏分含有C12+伯醇。
10.权利要求9的方法，其中较轻的馏分含有基本上全是C12-C24的伯醇。
11.权利要求6的方法，其中费-托方法的特征是非变换条件。
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