CN109642171A - 旨在供应锅炉或柴油发动机的包含特定的酯和烷烃的混合物 - Google Patents
旨在供应锅炉或柴油发动机的包含特定的酯和烷烃的混合物 Download PDFInfo
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- 238000011068 loading method Methods 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PSXNDMJWRZYVTM-UHFFFAOYSA-N octanoic acid butyl ester Natural products CCCCCCCC(=O)OCCCC PSXNDMJWRZYVTM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C10L10/00—Use of additives to fuels or fires for particular purposes
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Abstract
本发明的目的是用于锅炉或柴油发动机的液体燃料与特定的长链酯和烷烃的混合物,以及其用于在锅炉或柴油发动机运作期间减少颗粒和氮氧化物排放的用途。
Description
技术领域
本发明涉及一种用于锅炉或柴油发动机燃料的可燃液体基混合物,其包含在其操作期间减少锅炉和柴油发动机的颗粒和氮氧化物排放的特定化合物。
背景技术
从对抗温室气体的角度,柴油发动机是有效的发动机,因为在相同功率下,它们比汽油发动机排放的温室气体少约20%。同样,由于某些对人体有害的排放,特别是颗粒和氮氧化物排放,它们日益受到批评。在一些主要的城市中心,甚至一些整个地区,这些排放引起的空气污染构成主要问题。
在许多国家,柴油发动机的颗粒和氮氧化物排放受到监管。在欧洲尤其如此,其中法条规定的限制日益严格(目前为Euro6标准)。其他主要国家,特别是美国也是如此,但在一些州,例如加州空气资源委员会管理的州,限制非常低。
对颗粒进行两类测量:
·表征废气颜色的测量值(烟雾测量);和
·颗粒重量、直径和计数的测量。
粒径是多变的。通常,公认四类小颗粒:直径小于10μm的PM10,直径小于2.5μm的PM2.5,直径小于0.1μm的超细颗粒和特征在于直径小于50nm的纳米颗粒。
柴油发动机排放的大多数颗粒的直径小于1μm。因此,它们代表细或超细颗粒和纳米颗粒的混合物。认为最小的对人类最危险。
30年来,柴油发动机通过提高燃料质量(降低硫含量)、改进燃烧过程(喷射系统的优化)和改进废气处理方法(例如废气再循环、催化氧化系统和颗粒过滤器),取得了明显进步。尽管30年来新发动机的颗粒排放减少了98%,但认为颗粒问题足够严重,以致一些城市中心已经达到了他们想要在城市中禁止柴油车辆的程度。这特别是由于以下事实:柴油车辆维持多年(个人车辆为8-10年,卡车和公共汽车通常超过15年)。
除了新车辆的减排措施和替代能源的推广(例如电动车辆或天然气车辆)之外,找到现有柴油发动机车辆的解决方案将是非常有用的。
用于锅炉的液体燃料遭遇颗粒和氮氧化物排放的相同问题,特别是对于旧的锅炉,其对颗粒和氮氧化物污染的贡献也非常显著。
本发明的目的是解决这些问题,特别是提供一种简单、有效和经济的用于减少柴油发动机和液体燃料锅炉的排放的解决方案。
为此目的,本发明提出除了可能已经存在于燃料中的那些之外,还将一种或多种特定的酯和一种或多种特定的烷烃一起加入柴油发动机燃料或锅炉燃料中。
在20世纪90年代之前,不存在柴油发动机的生物燃料,而乙醇已经在汽油中使用了很长时间,特别是在巴西和美国。
从大约1992年开始,生物柴油(其是植物油的甲基(或乙基)酯)的使用开始在法国出现,然后在欧洲和全世界出现。今天,取决于通过醇进行酯交换的脂肪的来源,使用各种类型的酯:植物油、动物脂肪或回收的油炸锅油。它涉及脂肪酸酯,其链长主要包括16-18个碳原子。这些产品通常以低于8%的水平加入普通柴油燃料中,或者它们以20%或30%使用,或者作为例外,以纯净物在专属运输车队中使用。然而,使用这种混合物可以在颗粒减少方面实现的改进是有限的(减少了加入酯的比率的约一半)。此外,这些酯倾向于增加氮氧化物。它们受制于欧洲标准EN14214和世界其他地方的类似标准,并且尤其是出于这个原因,加入普通柴油燃料的比率通常限制在8体积%。
开始开发其他生物燃料,特别是来自生物质的烷烃,无论它们是植物油还是也具有16-18个碳原子的加氢处理的动物脂肪(用氢处理以消除氧原子),或来自生物质气化、随后是费-托合成的BTL(生物质到液体)类型的产物。仍然通过实验开发了其他溶液,例如来自热解的加氢处理的油和可以通过生物质的厌氧发酵随后进行Kolbe电解获得的烷烃(专利申请WO 2014/170603)。
这些烃令人关注,因为它们通常具有高十六烷值,这有助于减少NOx排放。然而,对颗粒的作用仍然有限。
此外,若干年来已经提出向燃料添加各种氧化化合物(例如醇或酯)—目的不是减少颗粒排放,而是改进其他功能(例如改进耐寒性、润滑能力、对农业的影响、对温室效应的影响等),例如:
-在柴油燃料中使用超过10%的乙醇,但这需要存在昂贵的添加剂;
-在柴油燃料中加入丁醇(例如:Energy Conservation and Management Vol 51,Issue 10,October 2010,Effects of butanol-diesel fuel blends on theperformance and emissions of a high-speed DI diesel engine);
-在汽油、柴油燃料或煤油中加入来自生物质厌氧发酵的酯(专利FR 2,757,539A1,Dupré-Kaplan,Use of esters as fuels or combustibles)。
还进行了在柴油燃料中使用醛的测试(Reducing the Emission of Particlesfrom a Diesel Engine by Adding an Oxygenate to the Fuel Environmental Scienceand Technology 39(16):6260-5·September 2005),其目标是减少排放的颗粒,但也被认为是危险的乙醛的排放极大增加了。
尽管如此,这些解决方案均没有产生减少锅炉和柴油发动机运作期间的颗粒排放和氮氧化物排放的令人满意的解决方案。
发明内容
本发明具体的目标是在选自柴油燃料和民用燃料油的柴油发动机或用于锅炉的液体燃料中加入:
-至少一种生物来源的酯,其链长为8-14个碳原子;和
-至少一种生物来源的烷烃,其链长为8-14个碳原子。
其中加入燃料的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,和其中加入燃料的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%。
在本发明的含义中,生物来源被理解为是指来自生物质即农业或森林植物或有机废物的产品。
应注意,由于基于质谱仪测量的C14同位素相对于分子中所有碳的比例的年代测定,生物来源的酯和烷烃可以区别于混合物中存在的石油来源的酯和烷烃。与最近的光合作用产生的产物相比,化石产品具有更小的C14浓度。
尽管酯将降低颗粒排放,但是根据本发明重要的是,除了可能已经存在于燃料中的那些,添加链长为8-14个碳原子的烷烃,因为这种方式可以避免氮氧化物排放的增加。
根据本发明的混合物是具有可变组成的液体混合物。
有利地,用这种混合物可以减少锅炉和柴油发动机运作期间的颗粒和氮氧化物排放而不会使其他排放物(例如一氧化氮、CO、未燃烧的烃、HC等)恶化。而且,通过本发明可以制备所述混合物,使其满足液体燃料的所有规定,特别是最难以满足的那些,具体是:闪点必须高于55℃并且计算的十六烷值必须大于46。此外,根据本发明的混合物可以保留柴油发动机燃料或用于锅炉的液体燃料的性质—例如耐寒性、粘度等。
所使用的酯和/或烷烃尤其可以是生物来源的,即,来自农业或森林生物质或形成有机废物的生物燃料,其还具有抵抗温室气体效应的优点。
本发明的其他特征和优点将从以下详细描述中显现出来。
因此,本发明的目的在于一种旨在供应锅炉或柴油发动机的混合物,包含:
–至少一种选自柴油燃料和民用燃料油的用于锅炉或柴油发动机燃料的液体燃料;和
–加入燃料的至少一种生物来源的酯,其链长为8-14个碳原子;和
–加入燃料的至少一种生物来源的烷烃,其链长为8-14个碳原子;
其中加入的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,优选5-50%,和其中加入的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%,优选5-50%。
混合物中存在的链长为8-14个碳原子的加入的酯可以选自具有这种大小的任何酯。优选地,它可以包括己酸乙酯(C8)、丁酸丁酯(C8)、戊酸丁酯(C9)、己酸丁酯(C12)和/或辛酸丁酯(C14)。优选地,它不包括高级脂肪醇的酯,即从植物油脂肪酸获得的醇,其例如通过氢化还原并且与短酸如甲酸或乙酸组合。
混合物中存在的链长为8-14个碳原子的加入的烷烃可以选自具有这种大小的烷烃(支链或非支链)。优选地,它可以包括癸烷、十二烷和十四烷。
根据本发明,通过具体选择链长为8-14个碳原子的酯,有利地可以继续满足用于柴油发动机燃料和锅炉燃料的所有当前规定,加入含量为1%-8%,排除酯的最大含量,因为以这种方式生产的酯不是符合EN14214标准的脂肪酸甲酯。因此,根据一个变体,本发明的目标是如前所述的混合物,其中链长为8-14个碳原子的酯占所述混合物的1体积%-8体积%。该混合物可以作为普通燃料分配于所有分配泵中。
此外,根据本发明使用的酯也可以较高的含量使用。因此,根据另一个变体,本发明的目标是如前所述的混合物,其中链长为8-14个碳原子的加入的酯占所述混合物体积的8%-80%,其将作为普通燃料分配(如果批准用于该用途),或作为用于专属运输车队的燃料。
优选地,混合物中存在的链长为8-14个碳原子的酯是由来自厌氧生物质发酵和通过醇酯化的挥发性脂肪酸获得的生物来源的酯。
同样地,优选这样的混合物:其中混合物中存在的链长为8-14个碳原子的加入的烷烃是通过Kolbe电解挥发性脂肪酸获得的烷烃,所述挥发性脂肪酸来自生物质的厌氧发酵(如申请WO2014/170603所述)或来自通过气化和费-托合成的生物质。
除了燃料、特定链长的酯和烷烃之外,根据本发明的混合物可以包含至少一种用于在锅炉或柴油发动机运作期间改进十六烷值和/或增加颗粒排放的减少和/或减少氮氧化物的排放的额外添加剂。它可以包括例如四硝基甲烷。
可以添加其他添加剂以改进混合物的其他功能,如耐寒性、粘度等。
根据本发明的混合物可以通过本领域技术人员的其他常规技术获得。优选地,它通过在单个罐中简单混合组分或在单个管中混合两种流体而获得。在大多数国家,这种混合必须在海关部门的控制下进行。
本发明具体的目标是生产如前所述的根据本发明的混合物的方法,其包括在至少一种选自柴油燃料或民用燃料油的液体锅炉燃料或柴油发动机燃料中加入:
-至少一种生物来源的酯,其链长为8-14个碳原子;和
-至少一种生物来源的烷烃,其链长为8-14个碳原子。
以如下方式:加入的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,和其中加入的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%。
优选地,混合在10-50℃的温度下在搅拌罐中或在通过横流混合来混合各种组分的装置中进行。
令人惊讶且有利的是,使用在柴油发动机燃料或锅炉燃料中加入特定的酯和烷烃的根据本发明的混合物,可以非常显著地减少颗粒排放,而不会使其他排放物恶化,特别是氮氧化物和其他排放物,例如CO、HC等。按质量和计数,颗粒减少水平是加入率的两倍(20%加入量为30%-40%;40%加入量为60%-80%;50%加入量为80%-90%),这对减少城市颗粒排放是相当大的优势。由于颗粒质量和计数平行减少,因此该过程不会增强更危险的较小颗粒。
因此,本发明的具体目的在于为锅炉或柴油发动机提供一种混合物,其包含:
–至少一种选自柴油燃料和民用燃料油的用于锅炉或柴油发动机燃料的液体燃料;和
–加入燃料的至少一种生物来源的酯,其链长为8-14个碳原子;和
–加入燃料的至少一种生物来源的烷烃,其链长为8-14个碳原子;
其中加入的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,和其中加入的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%。
特别地,本发明的目标是在锅炉或柴油发动机中使用混合物以在其操作期间减少颗粒排放和/或减少氮氧化物排放。有利地,本发明还可以改进燃料的十六烷值。
根据本发明的混合物可用于任何液体燃料锅炉和任何柴油发动机,特别是用于固定柴油发动机或安装在运输车辆或船只或工地重型设备或农业设备或小型民用设备如割草机或旋耕机中的柴油发动机。
除了根据本发明的混合物之外,可以在锅炉和/或发动机中添加至少一种添加剂,其中所述添加剂能够在锅炉或柴油发动机运作期间改进十六烷值和/或增加颗粒排放的减少和/或减少氮氧化物的排放,和/或至少一种添加剂能够改进混合物的其他功能,如耐寒性、粘度等。
具体实施方式
现在通过根据本发明混合物的实施例和显示其有效性的发动机测试台上的排放测试结果阐述本发明。
所测试的各种混合物的组成描述于表中(具有各种加载率的实施例1-5,其表示与标称转数相比的发动机的RPM数)。这些混合物通过在罐中简单混合组分并手动搅拌而获得。
通过Horiba 9100(CO、CO2、O2、HC和NOx)和PPS PEGASOR颗粒分析仪在雷诺品牌汽车发动机的排气装置上进行测量。
获得的结果如下表所示:
这些结果表明,烷烃对颗粒排放没有显著的有利影响,而酯和烷烃一起出乎意料地能够非常显著地将颗粒减少至或多或少与酯含量成比例(颗粒下降是加入的酯含量的约两倍),同时显著降低NOx。在这方面,实施例5非常有说服力。
其他参数(CO、HC)没有退化。甚至CO显著下降。因此通过调节酯和烷烃的含量,可以优化柴油发动机的排放。
Claims (15)
1.一种旨在供应锅炉或柴油发动机的混合物,包含:
–至少一种选自柴油燃料和民用燃料油的用于锅炉或柴油发动机燃料的液体燃料;和
–加入燃料的至少一种生物来源的酯,其链长为8-14个碳原子;和
–加入燃料的至少一种生物来源的烷烃,其链长为8-14个碳原子;
加入的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,和其中加入的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%。
2.根据权利要求1所述的混合物,其特征在于链长为8-14个碳原子的酯占所述混合物体积的5-50%。
3.根据前述权利要求之一所述的混合物,其特征在于加入的链长为8-14个碳原子的烷烃占所述混合物的5-50体积%。
4.根据前述权利要求之一所述的混合物,其特征在于混合物中加入的链长为8-14个碳原子的烷烃是通过Kolbe电解来自生物质厌氧发酵的挥发性脂肪酸获得的烷烃或来自通过气化和费-托合成的生物质的烷烃。
5.根据前述权利要求之一所述的混合物,其特征在于混合物中的链长为8-14个碳原子的酯是其中从来自厌氧生物质发酵和通过醇酯化的挥发性脂肪酸获得酸部分的酯。
6.根据前述权利要求之一所述的混合物,其特征在于其包含至少一种可以在锅炉或柴油发动机运作期间改进十六烷值和/或减少颗粒排放和/或减少氮氧化物排放的额外添加剂。
7.根据前述权利要求之一所述的混合物,其特征在于其包含至少一种能够改进耐寒性和/或粘度的添加剂。
8.一种生产根据前述权利要求之一所述的混合物的方法,其包括在至少一种选自柴油燃料或民用燃料油的液体锅炉燃料或柴油发动机燃料中加入:
-至少一种生物来源的酯,其链长为8-14个碳原子;和
-至少一种生物来源的烷烃,其链长为8-14个碳原子,
以如下方式:加入的链长为8-14个碳原子的酯占所述混合物的1体积%-80体积%,和其中加入的链长为8-14个碳原子的烷烃占所述混合物的1体积%-80体积%。
9.根据权利要求1-7之一所述的混合物供应锅炉或柴油发动机的用途。
10.根据权利要求9所述的在锅炉或柴油发动机中的用途,用于降低锅炉或发动机运作期间的颗粒排放。
11.根据权利要求9或10所述的在锅炉或柴油发动机中的用途,用于降低锅炉或发动机运作期间的氮氧化物排放。
12.根据权利要求9-11之一所述的在锅炉或柴油发动机中的用途,用于改进燃料的十六烷值。
13.根据权利要求9-12之一所述的在锅炉或柴油发动机中的用途,其中添加其他添加剂以改进十六烷值或增强颗粒或氮氧化物排放的减少。
14.根据权利要求9-13之一所述的在柴油发动机中的用途,其中添加其他添加剂以改进耐寒性和/或粘度。
15.根据权利要求9-14之一所述的用途,用于固定柴油发动机或安装在运输车辆或船只或工地重型设备或农业设备或小型民用设备中的柴油发动机。
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PCT/EP2017/064432 WO2017216171A1 (fr) | 2016-06-13 | 2017-06-13 | Melange destiné à alimenter une chaudière ou un moteur diesel comprenant du gazole ou du fioul domestique ainsi que des esters et des alcanes provenant de la transformation de la biomasse |
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- 2017-06-13 CA CA3027314A patent/CA3027314A1/fr not_active Abandoned
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- 2017-06-13 US US16/309,555 patent/US20190309232A1/en not_active Abandoned
- 2017-06-13 EP EP17734253.2A patent/EP3469045A1/fr active Pending
- 2017-06-13 BR BR112018075781-0A patent/BR112018075781A2/pt not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2942804B1 (fr) * | 2009-03-09 | 2011-08-19 | Arkema France | Carburant aviation contenant une proportion de composes organiques ex-biomasse |
US20110154728A1 (en) * | 2009-12-29 | 2011-06-30 | Allison Felix-Moore | Fuel formulations |
WO2013083596A1 (en) * | 2011-12-05 | 2013-06-13 | Shell Internationale Research Maatschappij B.V. | New use |
US20140273118A1 (en) * | 2013-03-15 | 2014-09-18 | Virent, Inc. | Processes for Converting Biomass-Derived Feedstocks to Chemicals and Liquid Fuels |
Also Published As
Publication number | Publication date |
---|---|
US20190309232A1 (en) | 2019-10-10 |
EP3469045A1 (fr) | 2019-04-17 |
FR3052459A1 (fr) | 2017-12-15 |
CN109642171B (zh) | 2021-09-17 |
BR112018075781A2 (pt) | 2019-03-26 |
WO2017216171A1 (fr) | 2017-12-21 |
FR3052459B1 (fr) | 2020-01-24 |
CA3027314A1 (fr) | 2017-12-21 |
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