CN100587043C - 低硫柴油燃料和航空涡轮燃料 - Google Patents
低硫柴油燃料和航空涡轮燃料 Download PDFInfo
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- CN100587043C CN100587043C CN200480009730A CN200480009730A CN100587043C CN 100587043 C CN100587043 C CN 100587043C CN 200480009730 A CN200480009730 A CN 200480009730A CN 200480009730 A CN200480009730 A CN 200480009730A CN 100587043 C CN100587043 C CN 100587043C
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- 239000000446 fuel Substances 0.000 title claims abstract description 124
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 77
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000005864 Sulphur Substances 0.000 title claims abstract description 11
- 239000003350 kerosene Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000005194 fractionation Methods 0.000 claims abstract description 12
- 239000004071 soot Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 38
- 239000012188 paraffin wax Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 13
- 230000008014 freezing Effects 0.000 claims description 13
- 238000003380 quartz crystal microbalance Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 239000000779 smoke Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 2
- 238000005498 polishing Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000010779 crude oil Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 230000009183 running Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000013028 emission testing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
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Abstract
一种由低温费-托(LTFT)原料生产合成的低硫柴油燃料和低烟灰排放的航空燃料的方法,是通过分馏以体积比1∶2-5∶4将低温费-托原料分馏为一轻质煤油馏分和一重质柴油馏分,从而通过该方法生产航空燃料和柴油燃料。
Description
技术领域
本发明涉及一种低硫柴油燃料和一种航空燃料以及一种用于航空燃料的调合油料。
背景技术
在本说明书中,涉及低温费-托合成(LTFT)方法。这种LTFT方法是一种众所周知的方法,在该方法中,通过含有铁、钴、镍或钌的催化剂,一氧化碳和氢气反应生成范围从甲烷到蜡的直链烃和支链烃的混合物以及少量的含氧化合物。这种烃的合成方法基于费-托反应:
2H2+CO→~[CH2]~+H2O其中,~[CH2]~是烃产物分子的基本组成单元。
在工业上,LTFT方法用于将来自煤炭、天然气、生物资源或重油的合成气转化为从甲烷到分子量在1400以上的烃类物质。而术语“气到液”(GTL)方法是指基于天然气,即甲烷,以获得合成气的方案,一旦合成条件和产品加工是确定的,合成产品的品质基本上是相同的。
当主要产品是线性链烷烃时,其它产物,例如支链链烷烃、烯烃和含氧组分可构成产品分布的一部分。精确的产品分布取决于反应器构型、操作条件及所采用的催化剂,如Catal.Rev.-Sci.Eng.,23(1&2),265-278(1981)or Hydroc.Proc.8,121-124(1982)等文章中清楚描述的。
生产较重的烃类物质的优选的反应器为淤浆床或管式固定床反应器,而操作条件优选在160-280℃的范围内,在有些情况下,在210-260℃的范围内;压力为18-50巴,在有些情况下,优选20-30巴。
催化剂可含有活性金属,例如,铁、钴、镍或钌。而每一种催化剂都有其独特的产品分布,在所有的情况下,产品分布中都包括一些蜡状的高链烷烃物质,这些物质需要经进一步改质为可用产品。LTFT产物能够加氢转化为一系列最终产物,例如,中间馏分、石脑油、溶剂、润滑油基础油等。这种加氢转化,通常由一系列的过程组成,例如,加氢裂化、加氢处理和蒸馏,这种加氢转化可称为一种LTFT产物加工方法。通常,该方法设置为仅有两种液体产物传输至贮藏库。在大多数情况下,该方法还有少量的包含至多四个碳原子的轻烃副产物。典型的LTFT液体产物的性质见表1。
表1、典型的LTFT液体产物的性质
LTFT石脑油 | LTFT柴油 | |
密度,kg/l(20℃) | 0.685 | 0.765 |
蒸馏 | ||
■IBP,℃ | 54 | 151 |
■T10,℃ | 81 | 182 |
■T50,℃ | 101 | 249 |
■T90,℃ | 120 | 317 |
■FBP,℃ | 131 | 334 |
组成,wt% | ||
■正构链烷烃 | 59.0 | 31.9 |
■异构链烷烃 | 38.2 | 67.1 |
■环烷烃 | ND | ND |
■芳烃 | 0.3 | ND |
■烯烃 | 2.5 | ND |
■氧化物 | ND | ND |
异构链烷烃/正构链烷烃 | 0.65 | 2.10 |
申请人已确定有直接利用LTFT燃料,包括GTL燃料,而不与裂化物料混合,作为一种能够与常规的柴油燃料互换的燃料的需要。
根据英国航空涡轮燃料防卫标准91-91(DEF STAN 91-91)的规定,半合成航空燃料已于1999年被批准。
因而,在航空工业中对于作为燃料和/或燃料调合料的能够满足或超过上述标准的合成燃料,以及允许使用LTFT产品,包括GTL产品,或其组分的合成燃料的需求已得到确认。
发明内容
根据本发明的第一个方面,提供了一种由低温费-托(LTFT)原料生产合成的低硫柴油燃料和航空燃料的方法,该方法包括将低温费-托原料分馏为一种作为航空燃料和/或一种航空燃料调合料的轻质煤油馏分,以及一种可作为合成的低硫柴油燃料和/或柴油燃料调合料的重质柴油馏分,所述的各种馏分基本符合柴油和航空燃料的规格。
令人惊讶的是,尽管经过深度的加氢处理,在不使用添加剂的情况下,所述柴油燃料能够满足润滑性能的规格。通常,本领域普通技术人员会认为,经过深度加氢处理的燃料是需要添加润滑性能改进剂的。
当生产一种轻质煤油馏分时,作为一种提高LTFT燃料能量密度并保持低温流动性能(CFPP-低温过滤堵塞实验)和润滑性能规格的方法已被确定,其中的轻质煤油馏分既可用于与由原油中得到的调合料进行调合以生产半合成航空燃料,也可以直接作为合成的航空燃料。
该方法包括分馏并除去至少33体积%的LTFT原料,以形成所述的航空燃料或终馏点约为270℃的调合料。
典型地,该方法包括分馏并除去45体积%,或者甚至是55体积%的该原料。
为了满足喷气燃料(Jet A-1)冰点-47℃的要求,所述轻质煤油馏分可被切割,切割点为270℃。此外,通过滚珠钢体润滑剂性能评价机(BOCLE)测定的煤油馏分的润滑性能也超过了预期。
根据本发明的第二个方面,提供了一种合成的低硫燃料或用于低硫燃料的调合料,所述燃料或调合料具有以下性质:
-氢含量13质量%至17质量%;
-异构链烷烃与正构链烷烃的质量比为2至5;
-芳烃含量小于0.1%m/m;
-按照IP309的冷滤点(CFPP)低于-5℃;
-20℃时的密度至少为0.780kg/l;以及
-总氧含量少于80ppm。
典型地,所述异构链烷烃与正构链烷烃的质量比为3至4。
所述异构链烷烃与正构链烷烃的质量比可以为3.7。
所述燃料或调合料的氢含量可以是约15质量%。
典型地,所述冷滤点低于-9℃。
令人惊讶的是,尽管经过深度加氢处理,在不使用添加剂的情况下,所述燃料满足润滑性能的规格要求。
有利地,与由原油中得到的低硫燃料相比,即使已除去其轻组分,燃料的排放性能未受到不好的影响。
所述燃料或调合料可以为一种LTFT柴油馏分。
所述调合料的40℃粘度可大于2cSt。
所述燃料或调合料的终馏点可大于330℃,典型地约为340℃。
所述燃料或调合料的初馏点可大于200℃,典型情况是大于250℃,在一些具体应用中,初沸点超过265℃。
按照本发明的第三个方面,提供了一种合成的航空燃料或用于半合成航空燃料的燃料调合料,所述调合料具有以下性质:
-氢含量为13质量%至17质量%;
-异构烷烃与正构烷烃的质量比为0.5至3;
-BOCLE润滑性能磨斑低于0.85mm;
-作为含氧化合物的氧含量低于50ppm;其中,
-作为C7-C12伯醇的氧含量低于50ppm;及
-作为C12-C24伯醇的氧含量低于50ppm。
作为含氧化合物的氧含量可低于约10ppm。
作为C7-C12伯醇的氧含量可低于约10ppm。
作为C12-C24伯醇的氧含量可低于约10ppm。
根据HPLC,所述合成航空燃料或燃料调合料可含有低于0.1%m/m的芳烃。
所述合成航空燃料或燃料调合料的烟点可大于50mm。
所述合成航空燃料或燃料调合料的20℃密度可约为0.75kg/l。
所述合成航空燃料或燃料调合料的冰点可低于-47℃。
典型地,所述异构烷烃与正构烷烃的质量比为1-2。
所述异构烷烃与正构烷烃的质量比可以为1.2或1.16。
所述氢含量可约为15质量%。
所述调合料可直接用作全合成航空燃料,而不需要与从原油中提取的燃料组分进行调合。
所述调合料可以为一种LTFT煤油馏分。
所述调合料在-20℃的粘度可低于8cSt,典型地是4cSt。
所述调合料的终馏点可大于200℃,典型地,约为270℃。
按照本发明的第四个方面,提供了一种包括如上所述的调合料的半合成航空燃料,所述半合成航空燃料具有如下性质:
-异构烷烃与正构烷烃的质量比为0.5至3;
-烟点大于35mm;及
-芳烃含量至少8%m/m。
所述半合成航空燃料的15℃密度可至少为0.775kg/l。
所述半合成航空燃料的烟点可大于50mm。
所述半合成航空燃料的冰点可低于-47℃。
典型地,所述异构烷烃与正构烷烃的质量比为1至2。
所述异构烷烃与正构烷烃的质量比可为1.8。
所述调合料的-20℃粘度可低于8cSt,或甚至低于4cSt。
用50体积%的LTFT煤油和由原油中提取的经脱硫和深度加氢的煤油作为调合物,按照美国材料试验学会(ASTM D1655)和英国航空涡轮燃料防卫标准91-91对于喷气燃料Jet A-1的规定,能够满足对于密度和芳烃含量的最低要求。
由于LTFT燃料几乎是仅由正构和异构烷烃组成的,LTFT煤油馏分可用作航空涡轮燃料的调合料。LTFT煤油实质上不含芳烃和环烷烃,可使其具有非常好的烟点数值(即,它产生极少的烟灰)。
按照本发明的第五个方面,提供了一种具有热稳定性的以及燃烧时具有低的沉积倾向的航空燃料,该燃料包括选自:如上所述的全合成航空燃料、半合成航空燃料及合成的航空燃料调合料中的一种或多种。
典型地,所述航空燃料和调合料在260℃时的热安定性管沉积评级低于1。
典型地,所述航空燃料的石英晶体微量天平(QCM)沉积低于3μg/cm2。
更典型地,在不添加抗氧剂的情况下,在140℃下进行QCM实验15小时,所述航空燃料的QCM沉积低于2μg/cm2。
按照本发明的第六个方面,提供了一种低烟灰排放的航空燃料,该燃料包括选自:如上所述的全合成航空燃料、半合成航空燃料及合成航空燃料调合料中的一种或多种。
典型地,在巡航条件下,航空燃料调合料的标准化颗粒数密度(normalized particulate number density)降低约33%,更典型地,在巡航条件下降低60%以及在空转条件下标准化颗粒数密度降低67%,更典型地,与有代表性的常规航空燃料相比,在空转条件下降低83%。
具体实施方式
下面参照具体实施方式描述本发明,所述具体实施方式是用来说明本发明的,而不是用来限制本发明的应用的。
实施例
低硫柴油燃料
对萨索尔淤浆蒸馏柴油(Sasol Slurry DistillateTMdiesel)或Sasol SPDTM柴油进行蒸馏,使其终馏点为270℃,以满足喷气燃料JetA-1的冰点为-47℃的要求。所得到的柴油燃料的性质和煤油燃料的性质列于表2,包括密度、粘度、高频往复运动装置(HFRR)和滚珠钢体润滑剂性能评价机(BOCLE)的润滑性能试验,以及柴油的冷滤点(CFPP)和煤油的冰点。
表2、Sasol SPDTM柴油、重质柴油馏分以及通过分馏得到的轻质煤油馏分的选定的燃料性质
SasolSPD<sup>TM</sup>柴油 | SasolSPD<sup>TM</sup>柴油1 | SasolSPD<sup>TM</sup>煤油1 | SasolSPD<sup>TM</sup>柴油2 | SasolSPD<sup>TM</sup>煤油2 | |||
产品收率 | 体积% | 100% | 45% | 55% | 55% | 45% | |
密度15℃ | ASTMD4052 | kg/l | 0.769 | 0.790 | 0.752 | 0.786 | 0.747 |
密度20℃ | ASTMD4052 | kg/l | 0.765 | 0.786 | 0.748 | 0.782 | 0.743 |
氢含量 | ASTMD5291 | 质量% | 14.97 | 14.62 | 15.00 | 14.68 | 14.87 |
馏程 | IBP | ℃ | 151 | 268 | 157 | 246 | 154 |
ASTM D86 | 10% | ℃ | 182 | 282 | 172 | 262 | 168 |
50% | ℃ | 249 | 300 | 203 | 289 | 191 | |
95% | ℃ | 325 | 336 | 267 | 333 | 254 | |
FBP | ℃ | 334 | 341 | 278 | 339 | 267 | |
闪点 | ASTM | ℃ | 58 | 114 | 50 | 122 | 45 |
D93 | |||||||
冰点 | ASTM5901 | ℃ | -15 | -42 | -48 | ||
CFPP | IP 309 | ℃ | -19 | -9 | -12 | ||
粘度-20℃ | ASTMD445 | cSt | 4.26 | 4.17 | |||
粘度40℃ | ASTMD445 | cSt | 2.00 | 3.90 | 3.31 | ||
润滑性能(HFRR) | ASTMD6079 | μm | 617 | 450 | 751 | 446 | 781 |
润滑性能(BOCLE) | ASTMD5001 | mm | 0.81 | 0.83 | |||
十六烷值 | ASTMD613 | 72 | 76 | 75 | |||
总热值 | ASTMD240 | MJ/kg | 46.96 | 46.55 | 47.13 | 46.97 | 47.24 |
净热值 | ASTMD240 | MJ/kg | 43.79 | 43.44 | 43.95 | 43.86 | 44.09 |
净热值 | ASTMD240 | MJ/1 | 33.50 | 34.13 | 32.88 | 34.25 | 32.75 |
作为含氧化合物的氧 | GC-MS | ppm | <6 | <6 | <6 | <6 | <6 |
作为C7-C12 | GC-MS | ppm | <6 | <6 | <6 | <6 | <6 |
伯醇的氧 | |||||||
作为C12-C24伯醇的氧 | GC-MS | ppm | <6 | <6 | <6 | <6 | <6 |
总氧含量 | GC-TCD | ppm | <80 | <80 | <80 | <80 | <80 |
表2中:
Sasol SPDTM柴油是全馏程的LTFT柴油
Sasol SPDTM柴油1是一种45%重馏分的LTFT柴油
Sasol SPDTM柴油2是一种55%重馏分的LTFT柴油
Sasol SPDTM煤油1是一种55%轻馏分的LTFT煤油馏分
Sasol SPDTM煤油2是一种45%轻馏分的LTFT煤油馏分
表3、Sasol SPDTM煤油馏分与来自原油的经脱硫和加氢处理的煤油馏分调合后的选定的燃料性质
*其原文是Microsep without SDA
**其原文是Water interfase rating
柴油馏分
所述45体积%重馏分柴油在不使用添加剂的情况下用作纯的Sasol SPDTM柴油性能优异。
根据EN590:1999柴油燃料规格,460μm的最大磨斑直径是允许的。总氧含量低于80ppm的Sasol SPDTM柴油的润滑性能显著提高,并能满足现行的规格要求,因为该柴油馏分具有更高的粘度,因而在不使用润滑性能改进剂的情况下改善流体动力润滑。
所述Sasol SPDTM柴油的闪点是高的,因为它具有较高的初馏点,但该柴油馏分的低温流动性能仍是好的。
根据Sasol SPDTM柴油的气相色谱质谱分析(GC MS)和气相色谱火焰离子化分析(GC-FID)结果,在分馏为煤油和柴油之前,其异构烷烃与正构烷烃的比率为2.2∶1(见图1)。所述55%重质柴油馏分的异构烷烃与正构烷烃的比率为3.71。
图1.Sasol SPDTM柴油的碳数分布
图2.Sasol SPDTM柴油的密度与不同程度的分馏的关系图
分馏Sasol SPDTM柴油得到一具有更高的密度(见图2)和能量密度的柴油,该柴油具有更好的燃料经济性和动力性。在分馏之后,还显示出了其它变化,包括在其润滑性能上的改进、更高的粘度和闪点。尽管所述柴油馏分比较重,其好的低温流动性能并没有显著降低。
重质柴油馏分的废气排放性能
将一种Sasol SPDTM柴油燃料中重质馏分的废气排放性能与那些全馏分Sasol SPDTM柴油及欧洲参考柴油燃料进行比较。采用一辆新式的欧洲客车进行实验。与符合现行EN590燃油规格的常规柴油相比,排放性能未受到不良影响,尽管与全馏分的Sasol SPDTM柴油相比,未燃烃类、一氧化碳和颗粒物的排放恶化了。与全馏分的SasolSPDTM柴油相比,Sasol SPDTM柴油燃料中重质馏分具有更高的体积能量含量,致使所测得的燃料消耗量有2%的改进。
试验车辆
型号:2002 BMW 320d sedan
试验重量:1474kg
发动机排量:1995cm3
缸径与冲程比:84/90mm
压缩比:17∶1
输出功率:110kW(4000转/分)
最大扭矩:330Nm(2000转/分)
燃料喷射系统:博世共轨
排气后处理:双氧化催化剂
排放证明:欧III(2000)
试验燃料
为了进行比较,测试了三种燃料:
EN590:一种满足欧洲EN590规格的常规柴油燃料,其硫含量<10mg/kg。
全馏程Sasol SPDTM柴油:初馏点150℃、终馏点335℃的SasolSPDTM柴油。
55体积%重Sasol SPDTM柴油馏分:一种重质Sasol SPDTM柴油馏分,包括经分馏除去45体积%煤油馏分后的剩余物。
有关燃料规格见上面的表2。
按照欧洲EC/ECE试验方法进行排放试验,并采用NEDC试验周期。在每次试验的准备阶段进行两次预运转。EN590和全馏分SasolSPDTM柴油分别进行三次试验,55体积%重质Sasol SPDTM柴油馏分进行两次试验。所述燃料依次进行试验,在更换燃料之后,车辆经预热并以120km/h的速度运行5分钟。
ECE R15城市循环、EUDC公路循环以及ECE R15+EUDC组合循环的结果见下面的表4、5和6。
试验结果也可见图3-8。
从所进行的排放试验,可以得出以下结论:
●与欧洲EN590参考柴油燃料相比,采用重质Sasol SPDTM柴油馏分不会对试验车辆的废气排放带来不利影响。HC和CO的排放比EN590燃料低,而NOX和颗粒物的排放基本相同。试验车辆已证实,所有受控制的排放物均在欧III的排放限制之内。
●与全馏分柴油相比,除去45体积%的该柴油的轻质部分使得HC、C0和PM的排放量增加。虽然HC和CO的排放仍低于欧洲EN590参考燃料,但PM的排放与欧洲EN590参考燃料相似,而有些比全馏分柴油高30%。
●与全馏分柴油相比,由于Sasol SPDTM柴油重质馏分的密度的提高使得在体积燃料消耗量方面有2%的改进。然而,与欧洲EN590柴油燃料相比,燃料消耗量仍然高约3%。
表4、ECE R15城市循环排放和燃料消耗量
表5、EUDC公路循环排放和燃料消耗量
表6、复合的ECE+EUDC循环排放和燃料消耗量
图3.综合的HC排放
图4.综合的CO排放
图5.综合的NOX排放
图6.综合的PM排放
图7.综合的CO2排放
图8.燃料消耗
图9.与EN5900相比55体积%重质Sasol SPDTM柴油的排放
图10.与全馏分Sasol SPDTM柴油相比55体积%重质Sasol SPDTM柴油的排放
航空燃料
参考上述针对低硫柴油燃料的表格和讨论。
粘度和冰点是用来从数量上描述航空燃料流动性的物理性质,因此,对于航空煤油仅规定了粘度的上限,全合成Sasol SPDTM煤油馏分符合该规定。按照防卫标准91-91(DEF STAN91-91)对于喷气燃料JetA-1所要求的冰点为-47℃,轻质45体积%的全合成Sasol SPDTM煤油馏分满足该要求,其冰点为-48℃(见表2)。相信按照自动化的ASTM5901试验方法所测定的这种低的冰点,是由于全馏分Sasol SPDTM柴油中含有的超过60质量%的异构烷烃和全合成Sasol SPDTM煤油馏分中含有的超过50质量%的异构烷烃所导致的。
由于飞机上的空间是非常宝贵的,所以一定量的燃料所含有的能量的数量是重要的。具有高体积能量含量的燃料可使贮存在固定体积内的能量最大化,因而可提供最长的航程。所指明的Sasol SPDTM煤油馏分的净重量能量含量高于规定的42.8MJ/kg(见表3)。
通过滚珠钢体润滑剂性能评价机(BOCLE)(ASTM D5001试验方法)所测定全合成Sasol SPDTM煤油馏分的润滑性能,其磨斑直径低于为喷气燃料Jet A-1所规定的最大磨斑直径,这一点是意想不到的。
脱硫后的由原油中得到的煤油与Sasol SPD
TM
煤油调合
根据明确批准的半合成喷气燃料,如Jet A-1,其芳烃含量不得低于8体积%。由于Sasol SPDTM柴油不含芳烃(<0.001质量%),以50/50的比率将45体积%的Sasol SPDTM煤油馏分与源自MeroxTM的脱硫后的由原油中得到的煤油调合。作为调合料的全合成Sasol SPDTM煤油(见表3)和脱硫煤油的一个例子,MeroxTM煤油及其调合油的性质也归纳于表3中。
用于调合的经Merox法脱硫处理的由原油中得到的煤油的密度为0.809kg/l(15℃),且半合成调合油的规定的密度范围是0.776kg/l(15℃)。调合油的芳烃含量超过8体积%的限制(见表3)。
以达到50体积%的脱硫后的由原油中得到的煤油物流与SasolSPDTM煤油调合,可满足对半合成喷气燃料在组成、挥发度、流动性、水分离特性、润滑性能和热安定性(JFTOT)方面的要求。调合油的蒸馏曲线见图11。
图11.Kero MeroxTM煤油、45%Sasol SPDTM煤油馏分及其50%的调合油
合成煤油与由原油中得到的喷气燃料进行调合已被核准,但有某些限制。这些限制包括单独从费-托过程中得到的合成煤油不含有合成的芳香族化合物。终馏点为270℃的轻质Sasol SPDTM煤油符合这些限制,也符合对于Jet A-1冰点为-47℃的要求。作为一种调合油,其密度和芳烃含量也要符合密度为0.775kg/l(15℃)、芳烃含量为8体积%的最低要求。
经深度加氢处理的由原油中得到的煤油与Sasol SPD
TM
煤油调合
制备调合比例高达50体积%的Sasol SPDTM柴油与经深度加氢处理的由原油中得到的煤油的调合油,以说明一种符合Jet A-1要求的具有热安定性的半合成喷气燃料,例如,冰点、密度和润滑性能。表3列出了一种50体积%调合有经深度加氢处理的煤油,例如,一种加氢裂化煤油馏分的调和油的性质。
热安定性
按照喷气燃料热氧化测试装置(JFTOT)ASTM D3241试验方法测定全合成航空燃料和半合成航空燃料(轻质Sasol SPDTM煤油馏分与经脱硫和深度加氢的由原油中得到的煤油的调合油)的热氧化安定性。在过滤器无压降的情况下,全合成和半合成航空燃料的目测管沉积评级小于1。
采用石英晶体微量天平(QCM)测得的热安定性结果证实了JFTOT的结果,即,在不使用抗氧剂的情况下,经140℃、15小时后仅有2μg/cm2的沉积。
采用JP-8+100热安定性改进添加剂进行试验未改进全合成航空燃料及其调合油的安定性,因该燃料的沉积物很少。
烟灰排放
在空转和巡航条件下,将全合成航空燃料及其调合油的有关颗粒物(烟灰)的燃气涡轮发动机试验结果与典型的常规航空燃料进行比较。在巡航条件下,全合成Sasol SPDTM轻质煤油馏分形成的烟灰比常规的JP-8航空燃料减少40%,而其调合油在巡航条件下形成的烟灰减少33%。
在空转条件下,与典型的常规航空燃料相比,Sasol SPDTM煤油调合料形成的烟灰减少83%,而其调合油在空转条件下形成的烟灰减少67%。
Claims (22)
1.一种由低温费-托原料生产合成的低硫柴油燃料和低烟灰排放的航空燃料的方法,所述方法包括将低温费-托原料以1∶2-5∶4的体积比分馏为一轻质煤油馏分和一重质柴油馏分,以形成烟点大于50mm、冰点低于-47℃、BOCLE润滑性能磨痕小于0.85mm、热安定性管沉积评级在260℃下小于1的用作低烟灰排放的航空燃料和/或航空燃料调合料的轻质煤油馏分,以及根据IP309的CFPP低于-5℃、20℃密度至少为0.78kg/l、40℃粘度大于2cSt的用作合成低硫柴油燃料和/或柴油燃料调合料的重质柴油馏分。
2.按照权利要求1所述的方法,其中,分离出至少33体积%的低温费-托原料,以形成终馏点为270℃的所述航空燃料或调合料。
3.按照权利要求2所述的方法,其中,该方法包括分馏和除去所述原料的45体积%,以形成所述航空燃料或调合料。
4.按照权利要求2所述的方法,其中,该方法包括分馏和除去所述原料的55体积%。
5.按照权利要求1-4中任意一项所述的方法,其中,所述轻质煤油馏分20℃密度为0.75kg/l。
6.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分的异构烷烃与正构烷烃的质量比为0.5-3。
7.按照权利要求6所述的方法,其中,由该方法所得到的轻质煤油馏分的异构烷烃与正构烷烃的质量比为1-2。
8.按照权利要求7所述的方法,其中,由该方法所得到的轻质煤油馏分的异构烷烃与正构烷烃的质量比为1.16-1.2。
9.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分的氢含量为13质量%-17质量%。
10.按照权利要求9所述的方法,其中,由该方法所得到的轻质煤油馏分的氢含量为15质量%。
11.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分为一种低温费-托煤油馏分。
12.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分-20℃的粘度低于8cSt。
13.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分的终馏点高于200℃。
14.按照权利要求13所述的方法,其中,由该方法所得到的轻质煤油馏分的终馏点为270℃。
15.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分的石英晶体微量天平沉积小于3μg/cm2。
16.按照权利要求1-4中任意一项所述的方法,其中,由该方法所得到的轻质煤油馏分在不添加抗氧剂的情况下,在140℃下进行15小时石英晶体微量天平试验的石英晶体微量天平沉积小于2μg/cm2。
17.按照权利要求1-4中任意一项所述的方法,其中,所述重质柴油馏分具有以下性质:
-异构烷烃与正构烷烃的质量比为2-5;
-芳烃含量小于0.1%m/m;及
-总氧含量小于80ppm。
18.按照权利要求17所述的方法,其中,异构烷烃与正构烷烃的质量比为3-4。
19.按照权利要求17所述的方法,其中,异构烷烃与正构烷烃的质量比为3.7。
20.按照权利要求1-4中任意一项所述的方法,其中,所述重质柴油馏分的CFPP低于-9℃。
21.按照权利要求1-4中任意一项所述的方法,其中,所述重质柴油馏分的终馏点高于330℃。
22.按照权利要求1-4中任意一项所述的方法,其中,当所述重质柴油馏分在压燃式发动机中燃烧时,其所产生的颗粒排放物实质上与欧洲EN590参考柴油燃料采用同样的发动机在同样的条件下所产生的颗粒排放物等量。
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US6369286B1 (en) * | 2000-03-02 | 2002-04-09 | Chevron U.S.A. Inc. | Conversion of syngas from Fischer-Tropsch products via olefin metathesis |
AU2002256642B2 (en) * | 2001-03-05 | 2006-10-05 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of middle distillates |
US6846402B2 (en) * | 2001-10-19 | 2005-01-25 | Chevron U.S.A. Inc. | Thermally stable jet prepared from highly paraffinic distillate fuel component and conventional distillate fuel component |
JP4150579B2 (ja) * | 2002-12-03 | 2008-09-17 | 昭和シェル石油株式会社 | 灯油組成物 |
-
2004
- 2004-04-07 CN CN200480009730A patent/CN100587043C/zh not_active Expired - Lifetime
- 2004-04-07 DE DE112004000624T patent/DE112004000624T5/de not_active Ceased
- 2004-04-07 ES ES200550066A patent/ES2275445B1/es not_active Expired - Fee Related
- 2004-04-07 WO PCT/ZA2004/000041 patent/WO2004090078A1/en active IP Right Grant
- 2004-04-07 JP JP2006509119A patent/JP5137399B2/ja not_active Expired - Fee Related
- 2004-04-07 GB GB0520487A patent/GB2415436B/en not_active Expired - Fee Related
- 2004-04-07 BR BRPI0409261-9A patent/BRPI0409261A/pt not_active IP Right Cessation
- 2004-04-07 AU AU2004227418A patent/AU2004227418B2/en not_active Ceased
- 2004-04-07 CA CA2521864A patent/CA2521864C/en not_active Expired - Lifetime
-
2005
- 2005-10-10 ZA ZA200508142A patent/ZA200508142B/en unknown
- 2005-10-19 US US11/256,285 patent/US7390397B2/en active Active
- 2005-11-10 NO NO20055313A patent/NO20055313L/no not_active Application Discontinuation
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Also Published As
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GB2415436A (en) | 2005-12-28 |
BRPI0409261A (pt) | 2006-03-28 |
US20090013590A1 (en) | 2009-01-15 |
NO20055313D0 (no) | 2005-11-10 |
US8183419B2 (en) | 2012-05-22 |
NO20055313L (no) | 2006-01-11 |
CN1780899A (zh) | 2006-05-31 |
JP5137399B2 (ja) | 2013-02-06 |
GB0520487D0 (en) | 2005-11-16 |
ES2275445B1 (es) | 2008-06-01 |
US7390397B2 (en) | 2008-06-24 |
US20060111599A1 (en) | 2006-05-25 |
WO2004090078A1 (en) | 2004-10-21 |
JP2006522859A (ja) | 2006-10-05 |
DE112004000624T5 (de) | 2006-02-16 |
CA2521864A1 (en) | 2004-10-21 |
AU2004227418A1 (en) | 2004-10-21 |
GB2415436B (en) | 2007-01-31 |
ZA200508142B (en) | 2007-01-31 |
AU2004227418B2 (en) | 2008-09-11 |
ES2275445A1 (es) | 2007-06-01 |
CA2521864C (en) | 2011-12-06 |
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