CN101163779A - Burning diesel fuel purifier - Google Patents

Burning diesel fuel purifier Download PDF

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Publication number
CN101163779A
CN101163779A CN 200680008705 CN200680008705A CN101163779A CN 101163779 A CN101163779 A CN 101163779A CN 200680008705 CN200680008705 CN 200680008705 CN 200680008705 A CN200680008705 A CN 200680008705A CN 101163779 A CN101163779 A CN 101163779A
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China
Prior art keywords
fuel
biodiesel
diesel fuel
diesel
cerium
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CN 200680008705
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Chinese (zh)
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詹姆斯·M·瓦伦丁
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克林迪塞尔技术公司
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Priority to US11/038,286 priority Critical patent/US20050160663A1/en
Priority to US11/038,286 priority
Application filed by 克林迪塞尔技术公司 filed Critical 克林迪塞尔技术公司
Publication of CN101163779A publication Critical patent/CN101163779A/en

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    • C10L1/10Liquid carbonaceous fuels containing additives
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
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    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/02Use of additives to fuels or fires for particular purposes for reducing smoke development
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/06Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/105General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
    • F01N3/106Auxiliary oxidation catalysts
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02DCONTROLLING COMBUSTION ENGINES
    • F02D19/00Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/0639Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed characterised by the type of fuels
    • F02D19/0649Liquid fuels having different boiling temperatures, volatilities, densities, viscosities, cetane or octane numbers
    • F02D19/0652Biofuels, e.g. plant oils
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02DCONTROLLING COMBUSTION ENGINES
    • F02D19/00Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures
    • F02D19/06Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed
    • F02D19/08Controlling engines characterised by their use of non-liquid fuels, pluralities of fuels, or non-fuel substances added to the combustible mixtures peculiar to engines working with pluralities of fuels, e.g. alternatively with light and heavy fuel oil, other than engines indifferent to the fuel consumed simultaneously using pluralities of fuels
    • F02D19/082Premixed fuels, i.e. emulsions or blends
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02MSUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/14Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding anti-knock agents, not provided for in subgroups F02M25/022 - F02M25/10
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/12Inorganic compounds
    • C10L1/1233Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C10L1/1241Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof metal carbonyls
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    • C10L1/1814Chelates
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    • C10L1/14Organic compounds
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    • F01N2430/00Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
    • F01N2430/04Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by adding non-fuel substances to combustion air or fuel, e.g. additives
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    • F01N3/023Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
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    • Y02T50/60Efficient propulsion technologies
    • Y02T50/67Relevant aircraft propulsion technologies
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Abstract

基于生物柴油和超低硫柴油机燃料的共混物的改进的柴油机燃料,特别是具有含有含燃料携带的催化剂(FBC)浓缩物的燃料添加剂。 Improved blend of biodiesel and ultra low sulfur diesel fuel, diesel fuel, particularly with a fuel additive containing a catalyst (the FBC) carried by the fuel-containing concentrate. 该催化剂优选地包含铂和/或铈和/或铁,且该超低硫柴油优选地含有小于10%的芳烃。 The catalyst preferably comprises platinum and / or cerium and / or iron, and the ULSD preferably contains less than 10% aromatics. 该生物柴油的用量为该共混物的约20%。 The amount of the biodiesel for about 20% of the blend.

Description

净化器燃烧的柴油机燃料技术领域本发明提供了基于生物柴油和低芳烃含量的超低硫柴油机燃料(diesel fuel)的共混物的改进的柴油机燃料,特别是具有含有含燃料携带的催化剂(fliel borne catalyst) ( FBC )的浓缩物的燃料添加剂。 BACKGROUND cleaner fuel burning diesel engine of the present invention provides an improved ultra-low sulfur diesel fuel (diesel fuel) based biodiesel and low aromatic content diesel fuel blend, comprising in particular a fuel-containing catalyst carried (fliel borne catalyst) (FBC) a fuel additive concentrate. 背景技术美国专利申请No. 10/290,798中,描述了一种低排放柴油机燃料,其包括JetA和FBC。 BACKGROUND OF THE INVENTION U.S. Patent Application No. 10 / 290,798, describes a low-emissions diesel fuel, and comprising JetA FBC. 美国专利申请No. 10/357,027中,描述了一种低排放柴油机燃料,其包括Jet A和FBC的乳液。 U.S. Patent Application No. 10 / 357,027, describes a low-emissions diesel fuel, including Jet A and FBC emulsion. 美国专利申请No. 10/401,367中,描述了一种低排放柴油机燃料,其包括JetA、生物柴油和FBC。 U.S. Patent Application No. 10 / 401,367, describes a low-emissions diesel fuel, comprising JetA, biodiesel and FBC. 这些燃料确实有效,但是存在对其他柴油机燃料的持续需求,由此提供在污染物产生方面,尤其是NOx和微粒排放方面的进一步降低。 These fuels really effective, but there is a continuing need for additional diesel fuel, thereby generating pollutant provided, in particular to further reduce the NOx and particulate emissions. 发明内容本发明的目的是提供一种改进的柴油机燃料以降低未燃烧的烃、 一氧化碳、微粒和NOx的排放。 Object of the present invention is to provide an improved diesel fuel to reduce unburned hydrocarbons, carbon monoxide, particulates and NOx emissions. 本发明的另一目的是提供一种燃料,其采用具有期望的氢/碳平衡的可再生资源材料,该燃料可以通过这种方式减少二氧化^f友排放,并且提供由于有害污染物的排放也得到控制而产生的燃料经济性。 Another object of the present invention is to provide a fuel which has the desired use of the hydrogen / carbon balance renewable resource material, the fuel can be reduced in this way dioxide emissions Friends ^ f, since the emissions of harmful pollutants and to provide a fuel economy is also controlled arising. 这些和其它目的通过本发明来实现,本发明提供了基于生物柴油和低芳烃含量的超低硫柴油机燃料的共混物的改进的柴油机燃料,特别是具有含有含燃料携带的催化剂(FBC)浓缩物的燃料添加剂的该共混物。 These and other objects are achieved by the present invention, the present invention provides an improved blend of ultra low sulfur diesel fuel based biodiesel and low aromatic content diesel fuel, in particular a fuel-containing catalyst comprising carried (the FBC) and concentrated the fuel additive composition of the blend. 下面将描述本发明的优选方面。 The following preferred aspects of the invention will be described.

具体实施方式本发明提供了基于生物柴油和低芳烃含量的超低硫柴油机燃料的共混物的改进的柴油机燃料,特别是具有含有含燃料携带的催化剂(FBC)浓縮物的燃料添加剂。 DETAILED DESCRIPTION The present invention provides an improved blend of ultra low sulfur diesel fuel based biodiesel and low aromatic content diesel fuel, particularly with a fuel additive comprising fuel-containing catalyst carried (the FBC) concentrate. 作为本发明的燃料共混物的主要组分,提供了低芳烃(LA)含量、超低硫柴油(ULSD)燃料。 As a main component of the fuel blends of the present invention, there is provided a low aromatic (LA) content, ultra low sulfur diesel (ULSD) fuel. 本文中使用的术语低芳烃含量的含义是,所述燃料的该组分具有小于10%的体积百分比的芳烃含量,且优选为1~8%,特别是在2~5%的范围。 The term low aromatic content as used herein meaning that the components of the fuel having a volume percentage of aromatic content less than 10%, and preferably 1 to 8%, in particular in the range of 2 to 5%. 下表显示了2号柴油和低芳烃的超低硫柴油LA ULSD 的常见分析组成,以及根据本发明的优选制剂(具有FBC和20%生物柴油的LAULSD)。 The following table shows the analysis of number 2 diesel and ultra low sulfur diesel LA ULSD low aromatic composition, and according to a preferred formulation of the invention (with FBC and 20% biodiesel LAULSD). 也可以采用具有相同基本功能的等价物和组成上变化最高达50%、优选小于20%、例如不大于10%的那些。 It may also be employed with the same basic functional equivalents and variations in composition up to 50%, preferably less than 20%, such as no greater than 10% of those. <table>table see original document page 4</column></row> <table><table>table see original document page 5</column></row> <table>本发明的低排放柴油机燃料的其它主要成分为在本领域中被称作"生物柴油,,的物质。生物柴油占所述柴油共混物的比例较小,通常为约1~35%, 例如,大约15~25%。共混物通常含有约20%的生物柴油,其中这种来自生物的燃料组分包括"基于单烷基酯的含氧燃料",即脂肪酸酯,优选为衍生自甘油三酸酯的脂肪酸,例如大豆油、低芥子酸菜籽油和/或牛脂。本文中使用的术语"脂肪酸酯"旨在包括其中容易除去醇部分的任意化合物,包括多元醇和取代的醇等,但是优选为挥发性醇,例如d-C4醇的酯(优选甲酯), 含有约8个或更多(例如8 ~ 22个)碳原子的脂肪酸的2-曱氧基乙酯和苄酯, 和这些酯的混合物。挥发性醇是非常期望的。曱酯是最优选的酯反应物。适宜的 Other major <table> table see original document page 4 </ column> </ row> <table> <table> table see original document page 5 </ column> </ row> <table> low emissions diesel fuel according to the present invention. component is referred to in the art as "biodiesel ,, substance. accounts for the small diesel biodiesel blend ratio is usually about 1 to 35%, e.g., from about 15 to 25%. blends usually it contains about 20% biodiesel, wherein this fuel component of biological origin include "mono alkyl ester-based oxygenated fuel", i.e., fatty acid esters, preferably fatty acids derived from triglycerides, such as soybean oil , low erucic acid rapeseed oil and / or tallow. as used herein, the term "fatty acid esters" is intended to include any compound wherein the alcohol portion is easily removed, including polyols and substituted alcohols, etc., but is preferably a volatile alcohol, e.g. d-C4 alcohol ester (preferably methyl ester) containing about eight or more (e.g. 8 to 22) carbon atoms in the fatty acid group of 2 Yue acrylate and benzyl acrylate, and mixtures of such esters. volatile alcohol is highly desirable. Yue esters are most preferred ester reactant. suitable 反应物可以通过重氮基烷烃和脂肪酸的反应来制备,或者来自脂肪和油中自然发生的脂肪酸的醇解。适宜的脂肪酸酯可以来自合成的或天然的、饱和的或不饱和的脂肪酸, 且包括位置异构体和几何异构体。适宜的优选的饱和脂肪酸包括羊脂酸、羊蜡酸、月桂酸、肉豆蔻酸、椋榈酸、硬脂酸、花生酸、山嵛酸、异肉豆蔻酸、 异真珠酸、肉豆蔻酸、羊脂酸、和反异花生酸(anteisoarachadic)。适宜的优选的不饱和脂肪酸包括肉豆蔻油酸、棕榈油酸、蓖麻油酸、亚油酸、油酸、 反油酸、亚麻酸、eleasteric、花生四烯酸、芥子酸、和生红酸。本发明中特 The reaction may be prepared by reaction of diazoalkane and a fatty acid, a fatty acid or an alcohol solution derived from fats and oils naturally occurring. Suitable fatty acid esters can be derived from synthetic or natural, saturated or unsaturated fatty acids, and includes positional isomers and geometric isomers. suitable preferred saturated fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, starlings palm acid, stearic acid, arachidic acid, behenic acid, isostearic myristic acid, isostearic pearl acid, preferably myristic acid, caprylic acid, arachidic acid and anteiso (anteisoarachadic). suitable unsaturated fatty acids include myristoleic, palmitoleic, ricinoleic, linoleic, oleic, elaidic, linolenic, eleasteric, arachidonic, erucic acid, acid red and green present invention Laid

别优选使用来自大豆油、棕榈油、红花油、菜籽油、低芥子酸菜籽油(低芥子酸)、和玉米油的脂肪酸混合物。 Particularly preferred to use from soybean oil, palm oil fatty acids, safflower oil, rapeseed oil, low erucic acid rapeseed oil (low erucic acid), and corn oil mixture. 所述脂肪酸可以直接使用、和/或氬化之后、和/或异构化之后、和/或纯化之后使用。 The fatty acid may be used directly after after, and / or of argon, and / or isomerization, after use and / or purification. 例如,油菜籽为C22脂肪酸提供了良好原料;d6-ds脂肪酸可以由牛脂、大豆油、或棉籽油来提供;且更短链的脂肪酸可以由椰子、棕榈仁、或巴巴苏油来提供。 For example, rapeseed provides a good starting material for the C22 fatty acids; d6-ds fatty acids can be provided by tallow, soybean oil, or cottonseed oil; more short chain fatty acids can be provided by coconut, palm kernel, or babassu oil. 猪油、橄榄油、花生油、芝麻油、和葵花籽油是脂肪酸的其它天然原料。 Lard, olive oil, peanut oil, sesame oil, sunflower oil and other natural sources of fatty acids. 生物柴油中包含的优选的酯为低级烷基酯,例如,大豆脂肪酸和/或牛脂脂肪酸的曱酯、乙酯、丙酯和丁酯,特别是曱酯。 Preferred esters for biodiesel comprising lower alkyl esters, e.g., soya fatty acid and / or tallow fatty acid esters of Yue, ethyl, propyl and butyl, especially Yue ester. 下面为国家生物柴油委员会(National Biodiesel Board)于2001年12月设定的生物柴油(B100) 的规格,该规格被也采用来澄清和定义本发明。 Here is the National Biodiesel Board (National Biodiesel Board) in December 2001 setting biodiesel (B100) specifications, the specifications are also used to clarify and define the invention. 由此,生物柴油定义为来自植物油或动物脂肪的长链脂肪酸的单烷基酯,用于压缩-点火(柴油)发动机。 Thus, biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, for compression - ignition (diesel) engines. 该规格适用于使用或者与柴油机燃料共混之前的纯的(100°/。)生物柴油。 This specification is suitable for use before or diesel fuel blended with pure (100 ° /.) Biodiesel. 对于具有80%的柴油机燃料的生物柴油的20%共混物(B20),美国存在大量的经验。 For the 20% blend (B20) of 80% biodiesel with diesel fuel, the presence of large American experience. 虽然可以使用生物柴油(B100),但具有柴油机燃料的大于20%生物柴油的共混物应当逐一评价,直到可获得进一步的经验。 , But greater than 20% biodiesel Although biodiesel (BlOO) diesel fuel having a blend should be evaluated individually, until further experience is obtained. 也可以采用具有相同基本功能的等价物和组成上变化最高达25%、优选小于10%的那些。 It may also be employed with the same basic functional equivalents and composition variations of up to 25%, preferably less than 10% of those. 在某些情况中,低至2°/。 In some cases, as low as 2 ° /. 的生物柴油可以与馏出物源(distillate origin ) 的98。 Biodiesel may effluent source (distillate origin) 98 and evaporated. /。 /. 柴油机燃料的共混物使用。 A blend of diesel fuel. 性能 ASTM方法 限制 单位闪点 D93 最低130 摄氏度水和沉积物 D2709 最大0.050 体积%运动粘度,40°C D445 1.9-6.0 毫米2/秒硫酸化灰分 D874 最大0.020 质量°/。 Properties ASTM Method Units Flash Point limit minimum D93 130 ° C maximum Water and Sediment D2709 0.050 vol% Kinematic viscosity, 40 ° C D445 1.9-6.0 mm 2 / s maximum sulfated ash ° 0.020 mass D874 /. 硫 D5453 最大15 ppmS 15级别 最大500 S 500级别 铜条腐蚀 D130 最大3号 十六烷值 D613 最小47 浊点 D2500 优选为-2"C或才良 摄氏度 告值(report) <table>table see original document page 7</column></row> <table> 1为了符合特殊运行条件,对单独的限制条件的调整可以在购买者、销售者和制造商之间达成。一种这类产品可以以商标BioDiesel从国家生物柴油委员会的成员处获得,且确定为"大豆油脂肪酸曱酯、菜籽油脂肪酸甲酯(RME)、牛脂脂肪酸曱酯"。制造商也称该燃料为"基于单烷基酯的含氧燃料,由植物油或动物脂肪获得的燃料"。据称含有11重量%的氧。他们将该产品描述为来自脂质源,CAS序号67784-80-9的曱基酯。该燃料携带的催化剂(FBC)包含可溶于燃料的铂和/或铈和/或铁。该铈和/或铁通常以2 ~ 25ppm的浓度使用,而该铂为0.05-2ppm,铈或4失的优选水平为2 ~ 10ppm,例如3 ~ 8ppm,而该铂 Sulfur D5453 15 ppmS 15 largest maximum level 500 S 500 the maximum level of copper strip corrosion D613 minimum 47 cetane number 3 D2500 D130 cloud point is preferably -2 "C degrees or Cailiang report value (report) <table> table see original document page 7 </ column> </ row> <table> 1 to meet specific operating conditions can be achieved for individual constraints adjusted between buyers, sellers and manufacturers. One such product available under the trade bioDiesel obtained from members of the national biodiesel Board, and is identified as "Yue soybean oil fatty acid ester, rapeseed oil fatty acid methyl ester (RME), tallow fatty acid ester Yue." manufacturers also said the fuel was "based on mono-alkyl ester the oxygenated fuel, obtained from animal fat or vegetable oil fuel. "reportedly contains 11% by weight of oxygen. they describe the product from lipid sources, CAS No. 67784-80-9 ester of Yue. this fuel carries catalyst (the FBC) comprising a fuel-soluble platinum and / or cerium and / or iron. the cerium and / or iron at a concentration of 2 ~ 25ppm is typically used, and the platinum 0.05-2ppm, preferably cerium or loss 4 level 2 ~ 10ppm, e.g. 3 ~ 8ppm, while the platinum ^f吏用水平为0.1 ~ 0.5ppm, 例如0.15ppm。铈和/或铁与铂的优选比例为75:1 ~ 10:1。所述LA ULSD组分通常以与所述脂肪酸酯的体积比为约2:1~约5:1,例如约4:1使用。共混物的整个范围为乂人50:1延伸到l:50,都具有一些益处。该共混物的LAULSD 燃料组分优选地含有50 - 1500ppm清洁剂,最高达约500ppm润滑性添加剂和0.1 ~ lppm的铂COD和5 ~ 20ppm油酸铈或辛酸铈。本发明的优点是, 该脂肪酸酯为LA ULSD增加了润滑性并降低了对单独的润滑性添加剂的需求。本发明的催化的共混物有效地降低了受规定的(regulated )排放污染物, 所述排放污染物为NOx、微粒、烃和一氧化碳。优选地,该燃料同时降低NOx和微粒,这是不寻常的组合。与2号柴油的基准相比,优选的共混物有效地实现至少4%或更高的NOJ争低和至少25%的微粒降低。更优选的水平 ^ F level officials with 0.1 ~ 0.5ppm, such as cerium and / or iron to platinum ratio preferably 0.15ppm to 75: 1 to 10: 1. The LA ULSD component is generally in a volume of the fatty acid ester ratio of about 2: 1 to about 5: 1, for example from about 4: 1 to use the entire range of blend qe person 50: 1 L to extend: 50, have some benefit LAULSD fuel component of the blend. points preferably comprises 50 - 1500ppm detergent, up to about 500ppm lubricity additive and 0.1 ~ lppm platinum COD and 5 ~ 20ppm or cerium octoate, cerium oleate advantage of the invention is that the fatty acid ester is increased LA ULSD. lubrication and reduces the need for a separate lubricity additive catalytic blend of the present invention effectively reduced by the requirement (regulated) emissions of pollutants, the pollutants discharge the NOx, particulates, hydrocarbons and carbon monoxide. preferably, the fuel while reducing NOx and particulates, which is unusual combination compared with the reference number 2 diesel fuel, preferably a blend of at least 4% effective to achieve higher or lower NOJ contention and at least 25% reduced particles. more preferably, the level of

为5 ~ 25%的N0X降低和20 ~ 60%的微粒降低。 And 20 to 60% reduction of the fine particle is reduced to 5 to 25% N0X. 通过在配备有柴油机微粒过滤器或柴油机氧化催化剂的发动机中使用该燃料,可以实现更高的微粒降低。 By an engine equipped with a diesel particulate filter or diesel oxidation catalyst used in the fuel, you can achieve higher reduction microparticles. 这些降低优选地在降低或不增加N02排放的同时获得。 These are preferably obtained reduced without increasing or decreasing simultaneously N02 emissions. 可以采用的优选清洁剂包含聚烯烃酰胺亚烃基胺(polyolefin amide alkyleneamine )(约65 ~ 80% ),且剩余部分为石油馏出物。 Preferred detergents may be employed comprise a polyolefin amide alkylene amines (polyolefin amide alkyleneamine) (about 65 to about 80%), and the remainder petroleum distillate. 也可以采用具有相同的基本功能的等价物。 Have the same basic functional equivalents may also be employed. 一种优选形式为可从Texaco获得的TFA-4690-C, 浓度为约50 - 300ppm,更窄地为75 - 150ppm,例如约IOOppm,对其提供了下列分析:<table>table see original document page 8</column></row> <table>可以釆用的优选润滑添加剂包括妥尔油脂肪酸,其可以作为包括油酸、 亚油酸等脂肪酸的混合物而商购获得。 <Table> table see original document page: for example, about IOOppm, their analysis provides the following 150ppm, - a preferred form is available from Texaco TFA-4690-C, a concentration of about 50 - 300ppm, more narrowly 75 8 </ column> </ row> <table> preferred lubricating additives may preclude include tall oil fatty acid, which may be commercially available as mixtures comprising oleic acid, linoleic fatty acids. 也可以采用具有相同的基本功能的等价物。 Have the same basic functional equivalents may also be employed. 一种优选形式为可从Texaco获得的TFA-4769,浓度为约25 ~ 500ppm, 例如约150 ~ 250ppm,对其提供了下列分析:<table>table see original document page 8</column></row> <table>具体的铈化合物为:乙酰丙酮化铈III、环烷酸铈m、以及辛酸铈、油酸铈和其它的皂类如硬脂酸盐、新癸酸盐、和辛酸盐(2-乙基己酸盐)。 A preferred form of TFA-4769, available from Texaco, a concentration of about 25 ~ 500ppm, for example from about 150 ~ 250ppm, its provides the following analysis: <table> table see original document page 8 </ column> </ row > <table> specific cerium compounds are: cerium III acetylacetonate, cerium naphthenate, m, and cerium octoate, cerium oleate and other soaps such as stearate, neodecanoate, octanoate, and ( 2-ethylhexanoate). 许多所述铈化合物为满足式:Ce(OOCR)3的三价化合物,其中R-烃,优选C2~C22,且包括脂肪族的、脂环族的、芳基和烷芳基。 Many cerium compounds to satisfy the formula: Ce (OOCR) 3, a trivalent compound, wherein R- hydrocarbon, preferably C2 ~ C22, and including aliphatic cycloaliphatic, aryl and alkaryl groups. 铈的优选浓度为燃料的2 ~ 15ppm铈w/v。 The preferred concentration of cerium is cerium 2 ~ 15ppm w fuel / v. 优选地,将铈以雍基油酸铈丙酸盐络合物(40重量% 的铈)的形式提供。 Preferably, the cerium to cerium oleate, Yong-yl propionate complex (40% cerium by weight) of form. 优选的水平为朝向该范围的下限。 The preferred level is towards the lower limit of the range. 具体的铁化合物为:二茂铁、含铁的和亚铁的乙酰丙酮化物、铁皂如辛酸盐和硬脂酸盐(通常,作为Fe (III)化合物商购获得)、五羰基铁Fe(CO)5、 环烷酸铁(ironnapthenate)、和妥尔油中脂肪酸铁。 Specific iron compounds are: ferrocene, and ferrous iron acetylacetonate, iron octoate salts and soaps such as stearates (typically, as Fe (III) compounds are commercially available), iron pentacarbonyl Fe (CO) 5, iron naphthenate (ironnapthenate), and tall oil fatty acid iron. 任何铂族金属组合物,例如,描述于Bowers等人的美国专利US4,891,050、 Epperly等人的美国专利US5,034,020、和Peter-Hoblyn等人的US5,266,093中的1,5-环辛二烯铂联苯(铂COD ),都可以用作铂源。 Any platinum group metal compositions, e.g., Bowers et al., Described in U.S. Patent No. US4,891,050, Epperly et al., U.S. Patent No. US5,034,020, and Peter-Hoblyn, et al. In US5,266,093 1,5-suberic alkenyl biphenyl platinum (platinum COD), can be used as source of platinum. 其它适宜的铂族金属催化剂组合物包括可商购获得的或者容易合成的铂族金属的乙酰丙酮化物、铂族金属的二苯亚曱基丙酮化物、和四胺賴金属络合物的脂肪酸皂,例如四胺油酸柏。 Other suitable platinum group metal catalyst compositions include commercially available or readily synthesized platinum group metal acetylacetonates, platinum group metal diphenylmethylene Yue acetonide group, fatty acid soap, and Lai tetraamine metal complex such as oleic acid tetraamine Bo. 铂的优选浓度为燃料的0.1 ~ 2.0ppm铂w/v( mg/1), 例如,最高达约1.0ppm。 The preferred concentration of platinum was 0.1 ~ 2.0ppm fuel platinum w / v (mg / 1), e.g., up to about 1.0ppm. 优选的水平为朝向该范围下限,例如0.15〜0.5ppm。 The preferred level is towards the lower limit of the range, e.g. 0.15~0.5ppm. 铂COD为添加到燃料中的铂的优选形式。 Platinum COD is the preferred form of the fuel added to the platinum. 铈或铁通常以提供2~25ppm的金属浓度使用,而铂为0.05 ~ 2ppm,其中铈或铁的优选水平为5 ~ 10ppm, 例如7.5ppm,并且柏以0.1〜0.5ppm,例如0.15ppm的水平使用。 Cerium or iron is generally to provide a concentration of from 2 to 25ppm of metal used, while platinum is 0.05 ~ 2ppm, preferably wherein levels of cerium or iron is from 5 ~ 10ppm, e.g. 7.5ppm, and Bo to 0.1~0.5ppm, for example, the level of 0.15ppm use. 铈和/或铁与钼的优选比例为75:1〜10:1。 Cerium and / or iron and molybdenum preferably the ratio is 75: 1~10: 1. 除了利用根据本发明的低排放燃料之外,将发动机定时(enginetiming) 延迟例如2 ~ 6°,可以进一步降低NOx,且柴油机微粒过滤器和/或柴油机氧化催化剂的使用可以提供对一氧化碳、未燃烧的烃和微粒的进一步降低。 With the addition to the low emission fuels of the present invention, the timing of the engine (enginetiming) delay e.g. 2 ~ 6 °, the NOx can be further reduced, and, and / or use of the diesel particulate filter can provide a diesel oxidation catalyst for carbon monoxide, unburned further reducing hydrocarbons and particulates. 根据本发明的低排放燃料可以以具有水的乳液来使用,其中用水将油相乳化,该水包含基于航空煤油的重量的1~30%的水。 May be an emulsion having a water to fuel used according to the present invention, low-emission, wherein the oil phase was emulsified with water, the water comprising from 1 to 30% of water based on the weight of the aviation kerosene. 优选形式中,该乳液主要为油包水型的,且除了上述其它组分之外还优选地含有表面活性剂、润滑性添加剂和/或腐蚀抑制剂。 In preferred form, the primary emulsion is a water-in-oil, and other components in addition to the above also preferably contain surfactants, lubricity additives and / or corrosion inhibitors. 在美国专利US 5,743,922中有对适宜的乳液形式和添加剂的讨论。 Discussion of suitable emulsion forms and additives are in U.S. Patent No. US 5,743,922. 每加入1%的水,油包水型乳液通常提供约1%的NOx 降低。 Each 1% of water, water-in-oil type emulsion typically provides about 1% NOx reduction. 技术的组合将提供比单独使用任一种更大的排放降低。 Combination of techniques will provide greater than either alone to reduce emissions. 所述铂/铈燃料携带的催化剂或者其它催化剂是优选的,但也是可选的。 The platinum / cerium fuel entrained catalyst or other catalysts are preferred, but it is also optional. 如果期望的话,可以采用脂肪酸酯的共混物和航空煤油的组合以获得良好效果而无需所述燃料携带的催化剂。 If desired, the blend compositions fatty acid esters and aviation kerosene can be employed to obtain a good effect of the catalyst without the fuel carried. 在上述任意实施方式中由此形成的燃料,可以与定时变化、 EGR、氧化催化剂或微粒过滤器一起使用以增强排放控制。 The fuel thus formed in any of the above embodiments, the timing variations can be used with the EGR, oxidation catalysts or particulate filters to enhance the emission control. 术语"柴油机微粒过滤器"的含义为,表示本领域中公知用作废气过滤器的那些设备,其通过在复杂的内部结构内捕获一部分微粒来降低微粒排 The term "diesel particulate filter" meaning, refers to those devices known in the art as exhaust gas filters that reduce particulate to a portion of the exhaust by capturing particulates within a complex internal structure

放。 put. 由于沉积物会聚积,因此必须将它们再生或者替换。 Since the deposits will accumulate, therefore they must be replaced or regenerated. 在加强过滤器操作的情况下,上述燃料携带的催化剂与也描述过的基础燃料一起使用时-形成本发明的燃料-使得能极大的降低排放。 In the case of reinforcing the filter operation, when used in conjunction with the fuel entrained catalyst base fuel is also described - forming the fuel of the invention - makes it possible to greatly reduce emissions. 术语"柴油机氧化催化剂"的含义为,表示本领域中公知用作气体处理催化剂的那些设备,其通过以使得与催化的表面接触代替柴油机微粒过滤器中进行的捕获微粒来减少微粒、烃和一氧化碳的排放。 Meaning of the term "diesel oxidation catalyst" is a representation that known in the art that the device as a gas treating catalyst, which reduces the particulate by the contact surface such that the catalyst instead of the captured fine particles of the diesel particulate filter, hydrocarbons and carbon monoxide emissions. 在加强氧化催还剂操作的情况下,上述燃料携带的催化剂与也描述过的基础燃料一起使用时- 形成本发明的燃料-使得能极大的降低排放。 In the case where the reinforcing agent further oxidation catalyst operation, when used in conjunction with the fuel entrained catalyst base fuel is also described - forming the fuel of the invention - makes it possible to greatly reduce emissions. 延迟发动机定时,例如约2 ~约6°,是用于降低NOx的已知工序,遗憾的是,其自身由于不良燃烧而导致污染物产生。 Delay the timing of the engine, for example, from about 2 to about 6 °, a known process for reducing the NOx, unfortunately, due to poor combustion itself cause pollutant generation. 这种折衷困扰了本领域,因为对排放的控制变得重要。 This compromise plagued this area because of the emission control becomes important. 本发明的优点是,通过使用本发明的燃料并结合一种或多种上述技术和/或将一部分废气与燃烧气体互混的废气再循环,可以实现降低的N(X和其它污染物。在以一种优选形式实施本发明时,提供了FBC,如美国专利US 6,003,303及其中引用的参考文献中所述的。本发明在舰船运输工具的运行中具有特别的用途,所述舰船运输工具被带到中央位置以定期例如每日补给燃料。在这种示例性的设置中,燃料中FBC催化剂金属的浓度期望地保持为4 ~ 10ppm。提供下列实施例以进一步阐述和解释本发明,并且所述实施例不以任何方式理解为限定本发明。除非另外指出,所有份数和百分比为重量的。实施例1使用Platinum Plus⑧燃料携带的催化剂(FBC )(以Pt COD加入0.15ppm Pt)和轻度催化的(3〜5克Pt)柴油机氧化催化剂(DOC)的净化器燃烧的生物柴油燃料共混物,相对于标准No.2D燃料的 Advantage of the invention is that, by using the fuel of the present invention in combination with one or more of the techniques described above and / or a portion of the exhaust gas is intermixed with the combustion exhaust gas recirculation, can achieve a reduction of N (X and other contaminants. In when the embodiment of the present invention in a preferred form, the FBC is provided, as described in U.S. Patent reference US 6,003,303 and the references of the present invention has particular utility in the operation of the vehicle in the ship, the ship transport the tool is brought to a central location, for example, a daily periodic refueling. in such an exemplary arrangement, the concentration of FBC catalyst metal fuel is desirably maintained at 4 ~ 10ppm. the following examples are provided to further illustrate and explain the present invention, the examples are not understood and catalyst (the FBC) in Example 1 using Platinum Plus⑧ fuel carried as limiting the present invention. unless otherwise indicated, all parts and percentages are by weight. embodiment (Pt COD added to 0.15ppm Pt) in any manner and (3 to 5 grams Pt) diesel oxidation catalyst lightly catalyzed (DOC) of the cleaner burning biodiesel fuel blends, with respect to the standard fuel No.2D 基准排放,产生了51%的微粒(PM )降低和9%的NOx的降低。这种组合具有在常规校车中受到规定的污染物的超过100磅/年的降低和在本地运载车辆中超过200磅/年的降低。 常力见的生物柴油可以增加2 ~ 4%的NOx。在校车、饮料和本地服务舰船中常用的1995 Navistar DT-466发动机上进行三次联邦瞬态试验循环(transient test cycle )。下表中列出了所采用的燃料。<table>table see original document page 11</column></row> <table> Reduce baseline emissions, produced a 51% reduction of particulate (PM) and 9 percent reduction of NOx. This combination has been specified in the conventional bus contaminants than 100 pounds / year and more than 200 in the local carrier vehicle reduce pounds / year. Chang Li biodiesel can see an increase of 2 to 4% of NOx. three times the federal transient test cycle (transient test on a popular 1995 Navistar DT-466 engine in the school bus, beverage and local services in ship cycle). the following table lists the used fuel. <table> table see original document page 11 </ column> </ row> <table>

在最初的两个试验序列中,将20%生物柴油的共混物与低芳烃的超低石危柴油(LA ULSD )和Platinum Plus® FBC (以Pt COD加入0.15% ppm Pt)结合,且该发动机配备有轻度催化的(3-5g/ft3) DOC。 In the first two test sequences, a blend of 20 percent biodiesel and low aromatic ultralow stone risk diesel (LA ULSD) and the Platinum Plus® FBC (Pt COD was added to 0.15% ppm Pt) in combination, and the engines are equipped with catalytic mild (3-5g / ft3) DOC. 此时,整体排放降低为66%的HC、 63%的CO、 9%的NOx、 51%的PM和95%的SOx。 At this time, to reduce the overall emissions of 66% HC, 63% of CO, 9% of the NOx, 51% and 95% of PM SOx. 在废气的NO2成分中也发现了超过60。 NO2 component in exhaust gas is also found more than 60. /。 /. 的降低,N02为强的肺部剌激物,且可以随着传统重催化的后处理设备而增加。 Reduction, N02 to a strong lung irritants, and can be as heavy cat conventional post-processing apparatus is increased. 试验过程采用了轻度催化的DOC,其降低了成本且使N02的形成最小化。 Experimental procedure employs mild catalyzed DOC which reduces cost and minimize formed N02. 这些试验验证了在来自Cummins和Detroit Diesel的发动机上更早的试验工作,其显示了采用Platinum Plus® FBC和No.lD或ULSD制得的净化器燃烧的生物柴油共混物始终如一地降4氐NOx和PM排^:的能力。 These tests verified the earlier test work on engines from Cummins and Detroit Diesel, which shows using Platinum Plus® FBC and No.lD or ULSD prepared cleaner burning biodiesel blend consistently drop 4 Di NOx and PM ^ row: capacity. 上述说明旨在教导本领域普通技术人员实施本发明,并非在于详述所有显然的改进和变化,这些对于本领域普通技术人员来说在阅读本说明书后将是明显的。 The above description is intended to teach those of ordinary skill in the present embodiment of the present invention, that is not apparent to detail all modifications and variations which those of ordinary skill in the art upon reading this specification will be apparent. 但是,全部这些显然的改进和变化都应包含在由权利要求限定的本发明的范围之内。 However, all of those obvious modifications and variations be included within the scope of the invention defined by the appended claims. 所述权利要求覆盖了任何排列组合下的所指明的组分和步骤,除非上下文中具体指出相反含义,所述组分和步骤有效地满足了本发明既定的目的。 The cover as claimed components and steps in any permutation and combination of the specified requirements, unless the context specifically stated to the contrary, the components and steps effectively meet the established object of the present invention.

Claims (4)

1、一种改进的柴油机燃料共混物,其包含生物柴油和低芳烃含量的超低硫柴油机燃料,特别是具有含有含燃料携带的催化剂(FBC)浓缩物的燃料添加剂。 1. An improved diesel fuel blend, ultra low sulfur diesel fuel containing biodiesel and low aromatic content, in particular a fuel additive comprising fuel-containing catalyst carried (the FBC) concentrate.
2、 根据权利要求1的柴油机燃料共混物,其中所述FBC包含铂和/ 或纟失、和/或4巿。 2, diesel fuel blend according to claim 1, wherein the FBC comprises platinum and / or loss of Si, and / or 4 market.
3、 根据权利要求1的柴油机燃料共混物,其包含15~20%的生物柴油。 3, a diesel fuel blend according to claim 1, which comprises 15 to 20% biodiesel.
4、 根据权利要求1的柴油机燃料共混物,其中所述低芳烃含量的超低硫柴油組分包含小于10体积%的芳烃。 4, diesel fuel blend according to claim 1, wherein the low aromatic content ultra-low sulfur diesel component contains less than 10% by volume of aromatics.
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