CN101321849B - 燃料制剂 - Google Patents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
本发明涉及在柴油机中使用的燃料制剂，它由植物油单醇酯和最多20wt％直链和支链链烷烃和链长为C5-C11的烯烃及链长为C2-C8的醇组成，其中通过气化生物物质和随后费-托合成来获得所述链烷烃、烯烃和醇，其中所述费-托合成不包括通过氢化工序对费-托馏分的任何处理，和该制剂的闪点＞55℃和密度＞820kg/m3。
Description
技术领域
本发明涉及燃料制剂，它由至少一种植物油单醇酯和最多20wt％的最终沸点最大为196℃的费-托合成的烃馏分(该烃馏分未经加氢工序处理，因此除了含有正链烷烃以外，还含有链长为C5-C11的烯烃及最多10wt％链长为C2-C8的醇)的混合物组成。
背景技术
常规的柴油燃料仍然主要由从矿物油获得的烃混合物组成。考虑到下述事实即全世界对柴油燃料的需求增加和原油储备及炼厂能力持续下降，因此尝试至少部分用可再生的原料来填补日益扩大的供应缺口。
直接使用动物和植物油作为燃料的尝试可能一直只是被看作孤立的解决方案，因为现有技术的当前状态排除了它们在内燃机中的直接使用。只有在大幅度改装车辆技术之后，它们的利用才满足现代环境保护的要求。
尽管不同植物和动物油与矿物烃的混合物(例如在专利GB2384004中所述的)克服了大幅度改装燃料体系的需求，但所使用的油高的最终沸点使它们尤其不能满足配有柴油机的车辆的颗粒排放日益下降的极限值。
燃料制剂的另一选择是用植物油单醇酯和短链醇的混合物替代大部分柴油燃料的矿物油烃馏分。在专利DE 3149170中描述了这一燃料的主要缺点是其制备要求复杂的混合技术。而且，即使只在短时间储存之后，该燃料也倾向于显示出各组分的分离。
通过与短链单醇例如甲醇、乙醇或丙醇酯交换，将可自由获得的油菜、大豆和棕榈油全部转化成相应的烷基脂肪酸酯，来实现明显的改进。在没有任何大的技术变化的情况下，这种在市场上相当普遍且
尽管如此，在世界燃料篇2002中关于第IV类柴油所要求的质量数值方面，生物柴油还具有一些局限性。这些局限性包括例如低的十六烷值、高的粘度和差的冷性能，这将减少其在冬天的可用性，
如WO03/004588中所述，通过共混生物柴油与由费-托合成获得的烃混合物，实现在日常条件下可用性的改进。正如在WO03/004588中通过例举的实施方案所述，生物柴油和费-托合成的柴油馏分的混合物以1∶4到4∶1的体积比用于这一目的。根据进一步的描述，在该方法中，将费-托柴油暴露于氢化条件下。这一处理的结果是，费-托馏分由98体积％链长为C8-C24的链烷烃和剩余部分2体积％具有相同链长分布的烯烃组成。在燃料生产中通常不使用也是在费-托合成中获得的最终沸点＜200℃的轻质烃馏分。
发明内容
本发明基于该技术问题获得了大致环境中性的安全、容易生产的燃料混合物，它在储存过程中稳定且满足世界燃料第IV篇针对适合于日常使用的柴油燃料的要求。
通过混合最多20wt％最终沸点＜200℃的费-托合成中的轻质烃馏分到生物柴油中，来满足在引言中提及的这类柴油燃料的目标。
具体实施方式
下面通过下述实施例和实验来阐述本发明。通过简单混合来获得本发明用于这一目的的燃料。这两种组分无限混溶。除了符合EN 590柴油燃料以外，商业菜籽油甲酯(RME)和来自费-托合成的各种沸点的烃馏分用于该制备过程。由于RME和费-托合成的产品的硫值接近于检测极限，因此使用硫含量尽可能低的柴油燃料，以便在废气检测中获得相当的结果。
本发明来自费-托合成的低沸点馏分含有73.1体积％正烷烃、5.3体积％异烷烃、12.5体积％烯烃和9.0体积％醇，其起始沸点为110 ℃和最终沸点为190℃。相比之下，所使用的重质费-托柴油馏分含有87.2体积％正烷烃、11.7体积％异烷烃和1.1体积％烯烃，其起始沸点为198℃和最终沸点为305℃。在使用VW beetle 1.9Tdi/74kW的发动机试验中，比较商业柴油和菜籽油甲酯(RME)与根据本发明由含有15重量％轻质费-托馏分的菜籽油甲酯(RME)(下文称为RME-15LF)和含有15重量％费-托柴油的菜籽油甲酯(RME)(下文称为RME-15DF)以及含有30重量％费-托柴油的菜籽油甲酯(RME)(下文称为RME-30DF)制备的试验混合物。
下表示出了与根据WO/03004588生产的混合物RME-15DF和RME-30DF和商业燃料柴油和RME相比，本发明的燃料的物理性能。表1中的数据表明闪点大于55℃的三种燃料混合物RME-15LF、RME-15DF和RME-30DF满足安全处理和储存的要求。由于测定到的密度和粘度值只有微小的变化，因此不可能出现燃料消耗的体积差异。
正如所预期的，燃料的十六烷值随所混合的正烷烃分数而增加。十六烷值是柴油燃料点火性的量度。若这一数值相对低，则较差的点火性导致较长的点火延迟，从而导致差的冷启动性能、高压峰值和因此较高的废气排放与噪音释放。
表1：物理性能
| 性能 | 单位 | 方法 | 柴油 | RME | RME-15LF | RME-15DF | RME-30DF |
| 十六烷值 | - | EN ISO 5165 | 55 | 51 | 60 | 63 | 63 |
| 15℃下的密度 | g/cm3 | EN ISO 3675 | 0.827 | 0.868 | 0.836 | 0.840 | 0.829 |
| 40℃下的粘度 | mm2/s | EN ISO 3104 | 3.023 | 4.411 | 3.129 | 3.295 | 2.980 |
| 闪点 | ℃ | EN ISO 2719 | 57 | 144 | 57 | 58 | 67 |
| CFPP | ℃ | EN 116 | -15 | -14 | -19 | -15 | -15 |
| 硫 | ppm | EN 20846 | 41 | 4 | ＜3 | ＜3 | ＜3 |
令人惊奇地，很明显与商业燃料柴油和RME以及参考混合物RME-15DF和RME-30DF相比，根据本发明生产的十六烷值为60的燃料混合物显示出在严寒中明显改进的启动行为。
根据表2和3的数据可以明显看出，本发明的燃料RME-15LF的表面张力几乎下降到柴油燃料的水平。当在供例举目的的发动机中使用 喷嘴直径为0.12mm的5孔喷嘴时，这种低表面张力导致明显改进的喷洒方式。
液滴尺寸分布朝较小液滴偏移，在柴油机启动时废气内存在的冷烟明显下降。未观察到注射喷嘴显示出后期滴流。而且，在燃烧室、注射器内和在15,000km的试验操作后在注射喷嘴内获得的铸件内表面检查结果表明，使用RME-15LF没有沉积物。不需要混合点火助剂例如二乙醚，而这对于在冬季操作柴油机来说是常见的。
表2：在不同温度下表面张力测量值
| 板法mN/m | 柴油 | RME | RME-15LF | RME-15DF | RME-30DF |
| 30℃ | 27.0 | 30.6 | 27.3 | 29.3 | 28.9 |
| 60℃ | 24.8 | 28.3 | 25.2 | 27.2 | 27.0 |
表3：液滴尺寸分布测量值
| 柴油 | RME | RME-15LF | RME-15DF | RME-30DF | |
| 最大频率vol.％/μm | 18 | 14 | 19 | 18 | 18 |
| 液滴直径，μm | 125 | 245 | 105 | 155 | 185 |
注射压力250bar，燃料温度30℃
而且，本发明所使用的燃料这一明显改进的燃烧行为导致燃烧噪音明显下降。正如表4所示，根据DIN 45635测定的86dBA的气载噪音总水平是所有测试燃料中最低的。不存在当发动机显示出明显的点火延迟时出现的“敲钉声音”。也没有观察到对热发动机的启动行为和运转平稳度的干扰，这是因为本发明燃料的一些组分沸点低的结果。
表4：燃烧噪音测量值
| 燃烧噪音 | 柴油 | RME | RME-15LF | RME-15DF | RME-30DF |
| dBA | 87 | 93 | 86 | 88 | 88 |
发动机速度2000rpm，燃料温度30℃
另外满足应用于试验车辆的欧3标准所要求的排放极限。令人惊奇地，所进行的试验表明颗粒排放下降效果明显。正如表5所示，对于燃料RME-15LF测定的烟灰值1.4明显低于其它燃料。由于所有RME-基燃料均可视为不含硫，因此对于柴油来说2.4的数值应当特别重要。
表5：烟灰值测量值
| 烟灰值 | 柴油 | RME | RME-15LF | RME-15DF | RME-30DF |
| 2.4 | 1.9 | 1.4 | 2.0 | 1.9 |
发动机速度2000rpm，有效的介质压力4bar，燃料温度30℃
在测定CFPP值中，与所测试的燃料不同，根据本发明制备的燃料明显降低到较低的温度。醇馏分抑制或防止蜡晶体生长及聚集。这一效果通常只是通过靶向添加聚合物基添加剂来实现。
总之，采用本发明的组合物涉及下述优点：保持费-托产品内的氧(oxo-)组分，与由植物油单醇酯制备且含有其中氧组分通过氢化工序被除去的费-托馏分的相当燃料混合物相比，观察到该燃料体系显示出明显较低的被污染倾向。燃料混合物明显下降的表面张力(这归因于在费-托产品内保留的氧组分)实现注射入燃烧室内的燃料的改进气化。该燃料组合物不包含芳族组分。尽管其硫含量非常低，但不需要润滑性改进添加剂。与常规的石化柴油燃料相比，若不小心泄漏，则只观察到对暴露的生态系统微小的有毒影响，且由于省去了氢化处理费-托馏分，提高了燃料生产的总效率。
因此，当在柴油机中使用时，在其它条件相同的情况下，根据本发明生产的燃料RME-15LF在安全、发动机负载和环境相容性方面显示出突出的优点。基于这一背景，这揭示了在柴油燃料市场中多种应用中引入费-托合成的轻质馏分的可能性，而所述费-托合成的轻质馏分在发动机中远未被有效利用。
Claims (6)
1.用于柴油机中的燃料制剂，它由植物油单醇酯和最多20wt％的最终沸点最大为196℃的费-托合成的烃馏分组成，其中通过气化生物物质和随后费-托合成来获得所述费-托合成的烃馏分，其中所述费-托合成不包括通过氢化工序对费-托合成的烃馏分的任何处理，因此所述费-托合成的烃馏分含有直链和支链链烷烃和链长为C5-C11的烯烃及最多10wt％的链长为C2-C8的醇，和该制剂的闪点＞55℃和密度＞820kg/m3。
2.权利要求1的燃料制剂，其特征在于在费-托烃中较高级醇的比例小于10体积％。
3.权利要求1或2的燃料制剂，其特征在于粘度小于或等于4mm2/s。
4.权利要求1或2的燃料制剂，其特征在于十六烷值大于52。
5.权利要求3的燃料制剂，其特征在于十六烷值大于52。
6.制备用于柴油车辆中的燃料制剂的方法，其特征在于混合植物油单醇酯与最多20wt％的最终沸点最大为196℃的费-托合成的烃馏分，其中通过气化生物物质和随后费-托合成来获得所述费-托合成的烃馏分，其中所述费-托合成不包括通过氢化工序对费-托合成的烃馏分的任何处理，因此所述费-托合成的烃馏分含有支链和直链的链烷烃和链长为C5-C11的烯烃及最多10wt％的链长为C2-C8的醇，其中该制剂的闪点＞55℃和密度＞820kg/m3。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005058534A DE102005058534A1 (de) | 2005-12-08 | 2005-12-08 | Kraftstoffzubereitung |
| DE102005058534.5 | 2005-12-08 | ||
| PCT/EP2006/010548 WO2007065512A1 (de) | 2005-12-08 | 2006-11-03 | Kraftstoffzubereitung |
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| Publication Number | Publication Date |
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| CN101321849A CN101321849A (zh) | 2008-12-10 |
| CN101321849B true CN101321849B (zh) | 2012-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006800458314A Active CN101321849B (zh) | 2005-12-08 | 2006-11-03 | 燃料制剂 |
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| Country | Link |
|---|---|
| US (1) | US7972392B2 (zh) |
| EP (1) | EP1966354A1 (zh) |
| CN (1) | CN101321849B (zh) |
| CA (1) | CA2631138C (zh) |
| DE (1) | DE102005058534A1 (zh) |
| MY (1) | MY148215A (zh) |
| NO (1) | NO20082284L (zh) |
| WO (1) | WO2007065512A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2009005723A (es) | 2006-12-01 | 2009-09-28 | Univ North Carolina State | Proceso para la conversion de biomasa a co mbustible. |
| ES2341194B1 (es) * | 2007-09-11 | 2011-04-26 | Francisco Angulo Lafuente | Metodo de obtencion de una parafina, mediante un proceso biologico con microorganismos, a partir de material organico y su metodo de refinado para ser utilizado como combustible. |
| US8152869B2 (en) | 2007-12-20 | 2012-04-10 | Shell Oil Company | Fuel compositions |
| CN101998986B (zh) | 2007-12-20 | 2014-12-10 | 国际壳牌研究有限公司 | 燃料组合物 |
| DE102008032957A1 (de) | 2008-07-12 | 2010-01-14 | Dinano Ecotechnology Llc | Verfahren zur Gewinnung von synthetischem Diesel |
| US8152866B2 (en) * | 2009-05-13 | 2012-04-10 | GM Global Technology Operations LLC | Synthetic diesel fuel compositions |
| CN102947426A (zh) * | 2010-05-06 | 2013-02-27 | 萨索尔技术(控股)有限公司 | 利用高链烷烃馏出燃料的柴油机喷射器结垢改善 |
| US9187385B1 (en) | 2011-10-07 | 2015-11-17 | InnoVerdant, LLC | Charcoal ignition fluid |
| US9976097B2 (en) | 2015-03-04 | 2018-05-22 | InnoVerdant, LLC | Charcoal ignition fluid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225666A (zh) * | 1996-08-02 | 1999-08-11 | 埃克森研究工程公司 | 颗粒排放量得到减少的合成柴油 |
| US6475375B1 (en) * | 1999-04-06 | 2002-11-05 | Sasol Technology (Pty)Ltd. | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3149170A1 (de) | 1980-12-15 | 1982-07-29 | Institut Français du Pétrole, 92502 Rueil-Malmaison, Hauts-de-Seine | Brennbare komposition, welche gasoel, methanol und einen fettsaeureester enthalten und als dieseltreibstoff brauchbar sind |
| AU1280299A (en) | 1997-10-28 | 1999-05-17 | University Of Kansas, The | Blended compression-ignition fuel containing light synthetic crude and blending stock |
| US20030126790A1 (en) | 2001-01-12 | 2003-07-10 | Mccoy Harrison | Biodiesel blended with ethanol additive |
| DE60239102D1 (de) * | 2001-07-02 | 2011-03-17 | Sasol Tech Pty Ltd | Biodiesel-fischer-tropsch kohlenwasserstoffgemisch |
| GB2384004B (en) | 2002-01-15 | 2006-08-23 | Nicholas Charles Mcphee | Fuel mixture |
| US20050210739A1 (en) * | 2004-03-09 | 2005-09-29 | Conocophillips Company | Blends of synthetic distillate and biodiesel for low nitrogen oxide emissions from diesel engines |
-
2005
- 2005-12-08 DE DE102005058534A patent/DE102005058534A1/de not_active Withdrawn
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2006
- 2006-11-03 US US12/095,978 patent/US7972392B2/en active Active
- 2006-11-03 MY MYPI20081865A patent/MY148215A/en unknown
- 2006-11-03 WO PCT/EP2006/010548 patent/WO2007065512A1/de active Application Filing
- 2006-11-03 CA CA2631138A patent/CA2631138C/en active Active
- 2006-11-03 EP EP06806670A patent/EP1966354A1/de not_active Withdrawn
- 2006-11-03 CN CN2006800458314A patent/CN101321849B/zh active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225666A (zh) * | 1996-08-02 | 1999-08-11 | 埃克森研究工程公司 | 颗粒排放量得到减少的合成柴油 |
| US6475375B1 (en) * | 1999-04-06 | 2002-11-05 | Sasol Technology (Pty)Ltd. | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
Also Published As
| Publication number | Publication date |
|---|---|
| MY148215A (en) | 2013-03-29 |
| US7972392B2 (en) | 2011-07-05 |
| DE102005058534A1 (de) | 2007-06-14 |
| US20080295396A1 (en) | 2008-12-04 |
| NO20082284L (no) | 2008-09-03 |
| CA2631138A1 (en) | 2007-06-14 |
| EP1966354A1 (de) | 2008-09-10 |
| CN101321849A (zh) | 2008-12-10 |
| WO2007065512A1 (de) | 2007-06-14 |
| CA2631138C (en) | 2014-01-28 |
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