EP0457589B1 - Compositions de combustible à caractéristiques de combustion augmentées - Google Patents

Compositions de combustible à caractéristiques de combustion augmentées Download PDF

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Publication number
EP0457589B1
EP0457589B1 EP91304405A EP91304405A EP0457589B1 EP 0457589 B1 EP0457589 B1 EP 0457589B1 EP 91304405 A EP91304405 A EP 91304405A EP 91304405 A EP91304405 A EP 91304405A EP 0457589 B1 EP0457589 B1 EP 0457589B1
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EP
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Prior art keywords
fuel
nitrate
fuels
ppm
range
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Revoked
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EP91304405A
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German (de)
English (en)
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EP0457589A1 (fr
Inventor
Lawrence Joseph Cunningham
Alexander Michael Kulinowski
Timothy James Henly
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Afton Chemical Corp
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Afton Chemical Corp
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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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development

Definitions

  • This invention relates to preservation of the environment. More particularly, this invention relates to fuel compositions and methods that reduce atmospheric pollution normally caused by the operation of engines or combustion apparatus on middle distillate fuels.
  • French Patent Specification 821211 describes motor fuels, especially diesel fuels, containing a combustion accelerator, in particular a mixture of dissolved aryl nitrates, to increase the cetane number of the fuel.
  • This invention involves the discovery, inter alia, that it is possible to reduce the amount of NO x or CO or unburned hydrocarbons released into the atmosphere during operation of engines or other combustion apparatus operated on middle distillate fuel by employing as the fuel a middle distillate fuel having a sulfur content of 500 ppm or less and having dissolved there in a combustion improving amount of at least one organic nitrate combustion improver consisting essentially of 2-ethylhexyl nitrate.
  • a middle distillate fuel having a sulfur content of 500 ppm or less and having dissolved there in a combustion improving amount of at least one organic nitrate combustion improver consisting essentially of 2-ethylhexyl nitrate.
  • this invention provides the use of at least one fuel-soluble combustion improver consisting essentially of 2-ethylhexyl nitrate, incorporated in a hydrocarbonaceous middle distillate fuel having a sulfur content of less than 500 ppm prior to combustion in a proportion of 1000 to 5000 parts by weight per million parts of fuel for reducing emissions of at least two of NO x , CO and unburned hydrocarbons during combustion of said fuel, having the distillation profile disclosed in claim 1 and page 6, in a diesel engine in the presence of air.
  • the hydrocarbonaceous middle distillate fuel preferably has a sulfur content of 100 ppm or less and most preferably no more than 60 ppm.
  • the middle distillate fuel is composed principally or entirely of fuels derived from petroleum by any of the usual processing operations.
  • the finished fuels may contain, in addition, minor amounts of non-hydrocarbonaceous fuels or blending components such as alcohols, dialkyl ethers, or like materials, and/or minor amounts of suitably desulfurized auxiliary liquid fuels of appropriate boiling ranges (i.e. between about 160 and about 370°C) derived from tar sands, shale oil or coal.
  • the sulfur content of the total blend must be kept below 500 ppm.
  • This invention thus provides improvements in the operation of motor vehicles and aircraft which operate on middle distillate fuels. These improvements involve fuelling the vehicle or aircraft with a hydrocarbonaceous middle distillate fuel having a sulfur content of less than 500 ppm (preferably 100 ppm or less and most preferably no more than 60 ppm) and containing the aforesaid organic nitrate combustion improver dissolved therein.
  • a hydrocarbonaceous middle distillate fuel having a sulfur content of not more than 500 ppm (preferably 100 ppm or less and most preferably no more than 60 ppm) and a 10% boiling point (ASTM D-86) in the range of about 154° to about 230°C, said fuel containing a minor combustion improving amount of at least one fuel-soluble organic nitrate combustion improver consisting essentially of 2-ethylhexyl nitrate.
  • Such fuel compositions tend on combustion to emit especially low levels of NO x . Without desiring to be bound by theoretical considerations, one explanation for such highly desirable performance is that fuels with higher 10% boiling points cause a delay in the progression of combustion and consequent higher peak temperatures which increase the amount of NO x formation.
  • a hydrocarbonaceous middle distillate fuel having a sulfur content of not more than 500 ppm (preferably 100 ppm or less and most preferably no more than 60 ppm) and a 90% boiling point (ASTM D-86) in the range of about 260° to about 320°C, said fuel containing a minor combustion improving amount of at least one fuel-soluble organic nitrate combustion improver consisting essentially of 2-ethylhexyl nitrate.
  • Such fuel compositions tend on combustion to emit especially low levels of particulates.
  • hydrocarbonaceous fuels utilized in the practice of this invention are comprised in general of mixtures of hydrocarbons which fall within the distillation range of about 160 to about 370°C. Such fuels are frequently referred to as “middle distillate fuels" since they comprise the fractions which distill after gasoline. Such fuels include diesel fuels, burner fuels, kerosenes, gas oils, jet fuels, and gas turbine engine fuels.
  • the used middle distillate fuels are those characterized by having the following distillation profile: °F °C IBP 250 - 500 121 - 260 10% 310 - 550 154 - 288 50% 350 - 600 177 - 316 90% 400 - 700 204 - 371 EP 450 - 750 232 - 399
  • Diesel fuels having a clear cetane number i.e., a cetane number when devoid of any cetane improver such as an organic nitrate) in the range of 30 to 60 are preferred. Particularly preferred are those in which the clear cetane number is in the range of 40 to 50.
  • the organic nitrate combustion improvers (also frequently known as ignition improvers) comprise nitrate esters of substituted or unsubstituted aliphatic or cycloaliphatic alcohols which may be monohydric or polyhydric.
  • Preferred organic nitrates are substituted or unsubstituted alkyl or cycloalkyl nitrates having up to about 10 carbon atoms, preferably from 2 to 10 carbon atoms.
  • the alkyl group may be either linear or branched (or a mixture of linear and branched alkyl groups).
  • nitrate compounds suitable for use as nitrate combustion improvery include, but are not limited to, the following: methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate
  • nitrate esters of alkoxy substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2-(2-ethoxyethoxy)ethyl nitrate, 1-methoxypropyl-2-nitrate, and 4-ethoxybutyl nitrate, as well as diol nitrates such as 1,6-hexamethylene dinitrate, and the like.
  • alkyl nitrates having from 5 to 10 carbon atoms, most especially mixtures of primary amyl nitrates, mixtures of primary hexyl nitrates, and octyl nitrates such as 2-ethylhexyl nitrate.
  • nitrate esters are usually prepared by the mixed acid nitration of the appropriate alcohol or diol. Mixtures of nitric and sulfuric acids are generally used for this purpose. Another way of making nitrate esters involves reacting an alkyl or cycloalkyl halide with silver nitrate.
  • the concentration of nitrate ester in the fuel can be varied within relatively wide limits such that the amount employed is at least sufficient to cause a reduction in emissions. This amount falls within the range of 1,000 to 5,000 parts by weight per million parts of fuel.
  • additives may be included within the fuel compositions of this invention provided they do not adversely affect the exhaust emission reductions achievable by the practice of this invention. Thus use may be made of such components as organic peroxides and hydroperoxides, corrosion inhibitors, antioxidants, antirust agents, detergents and dispersants, friction reducing agents, demulsifiers, dyes, inert diluents, and like materials.
  • the concentration was 2000 ppm of the organic nitrate.
  • the fuel contained 5000 ppm of the organic nitrate.
  • the fifth and final test involved another baseline run using the initial conventional DF-2 diesel fuel. In all instances the quantities of NO x , unburned hydrocarbons (“HC”), carbon monoxide (“CO”) and particulates emitted by the engine were measured and integrated. The results of these tests are summarized in the following table. The values shown therein for NO x , HC, CO, and Particulates, are presented in terms of grams per brake horsepower per hour (i.e. grams per 745 watts per hour). Thus the lower the value, the lower the rate and amount of emissions. Test No.
  • use of fuels having certain boiling characteristics as well as low sulfur levels results in still further reductions in either NO x or particulate emissions.
  • the emissions of NO x can be reduced to extremely low levels.
  • the low sulfur parameters set forth hereinabove and additionally having a 90% boiling point (ASTM D-86) in the range of 260-320°C particulate emissions tend to be reduced to especially low levels.
  • a Detroit Diesel Corporation Series 60 Engine in the 11.1 liter configuration and nominally rated at 320 hp at 1800 rpm was used in a series of emission tests.
  • the engine was installed in a heavy-duty transient emission cell equipped with a constant volume sampler (CVS) system.
  • CVS constant volume sampler
  • a dilution tunnel permitted measurements of HC, CO, NO x and particulates according to the EPA Transient Emissions Cycle Procedure.
  • the engine was started and warmed up. It was then run for 20 minutes at rated speed and load. Rated power was validated. In addition, a power test was conducted, mapping engine torque vs. speed. These parameters are required as part of the EPA Transient Cycle Procedure. Once this information was obtained, two 20-minute EPA Transient Cycles were run and engine controls were adjusted to meet statistical operating limits prescribed for the tests. The engine was shut down and allowed to soak for 20 minutes. At the end of the soak period, the Hot Start EPA Transient Cycle was run to measure NO x , CO and particulate emissions. A second emissions evaluation was conducted after another two-minute soak. Results for the two Hot Transient Cycles were averaged into a final reported value. Whenever a fuel was changed, new fuel was introduced into the fueling system, new fuel filters were installed, and fuel lines were flushed.
  • Fuels A through D were evaluated by the same Hot Start EPA Transient Emissions Cycle Procedure.
  • Fuels A, B, and C contained 2-ethylhexyl nitrate in an amount sufficient to raise the cetane number of the respective fuels to a nominal value of 50.
  • Fuel D which had a natural cetane number of 49.8 was used unadditized.
  • Fig. 1 presents graphically the results of NO x emissions in relation to the 10% boiling temperatures of the four fuels. It can be seen that the fuels in which the 10% boiling temperature was below 230°C had the lowest NO x emissions.
  • Fig. 2 The results of the particulate determinations are graphically depicted in Fig. 2. In this case, the results are shown as a function of 90% boiling temperatures of the base fuels. A trend toward lower particulate emissions with fuels having 90% boiling points within the range of 260-320°C was noted.
  • hydrodesulfurization is generally preferred, and includes a number of specific methods and operating conditions as applied to various feedstocks. For example, hydrotreating or hydroprocessing of naphthas or gas oils is generally conducted under mild or moderate severity conditions. On the other hand, sulfur removal by hydrocracking as applied to distillate stocks is usually conducted under more severe operating conditions.
  • Vacuum distillation of bottoms from atmospheric distillations is still another method for controlling or reducing sulfur content of hydrocarbon stocks used in the production of hydrocarbonaceous middle distillate fuels. Further information concerning such processes appears in Kirk-Othmer, Encyclopedia of Chemical Technology , Second Edition, Interscience Publishers, Volume 11, pages 432-445 (copyright 1966) and references cited therein; Idem. , Volume 15, pages 1-77 and references cited therein; and Kirk-Othmer, Encyclopedia of Chemical Technology , Volume 17, Third Edition, Wiley-Interscience, pages 183-256 (copyright 1982) and references cited therein. All of such publications and cited references are incorporated herein by reference in respect of processes or methods for control of reduction of sulfur content in hydrocarbonaceous middle disillate fuels or their precursor stocks.
  • Another method which can be used involves treatment of the hydrocarbonaceous middle distillate fuel with a metallic desulfurization agent such as metallic sodium, or mixtures of sodium and calcium metals.
  • a metallic desulfurization agent such as metallic sodium, or mixtures of sodium and calcium metals.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (8)

  1. Utilisation d'un agent améliorant la combustion, soluble dans les carburants, consistant essentiellement en nitrate de 2-éthylhexyle incorporé à un carburant consistant en un distillat moyen hydrocarboné, ledit carburant ayant le profil de distillation suivant : °C IBP 121-260 10% 154-288 50% 177-316 90% 204-371 EP 232-399
    et ayant une teneur en soufre inférieure à 500 ppm, avant combustion, en une proportion de 1000 à 5000 parties en poids par million de parties de carburant pour réduire les émissions d'au moins deux des composés consistant en NOx, CO et hydrocarbures imbrûlés au cours de la combustion dudit carburant dans un moteur diesel en présence d'air.
  2. Utilisation suivant la revendication 1, dans laquelle le carburant de base a une teneur en soufre égale ou inférieure à 100 ppm et un indice de cétane clair compris dans l'intervalle de 30 à 60.
  3. Utilisation suivant la revendication 1, dans laquelle le carburant de base a une teneur en soufre non supérieure à 60 ppm.
  4. Utilisation suivant la revendication 3, dans laquelle le carburant de base a un indice de cétane clair compris dans l'intervalle de 50 à 60.
  5. Utilisation suivant la revendication 3, dans laquelle le carburant de base a un indice de cétane clair compris dans l'intervalle de 40 à 50.
  6. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle les émissions de NOx, de CO et d'hydrocarbures imbrûlés sont réduites.
  7. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le carburant de base a un point d'ébullition à 10 % (ASTM D-86) compris dans l'intervalle de 154 à 230°C.
  8. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le carburant de base a un point d'ébullition à 90 % (ASTM D-86) compris dans l'intervalle de 260 à 320°C.
EP91304405A 1990-05-17 1991-05-16 Compositions de combustible à caractéristiques de combustion augmentées Revoked EP0457589B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US52449890A 1990-05-17 1990-05-17
US524498 1990-05-17
US61532290A 1990-11-19 1990-11-19
US615322 1990-11-19

Publications (2)

Publication Number Publication Date
EP0457589A1 EP0457589A1 (fr) 1991-11-21
EP0457589B1 true EP0457589B1 (fr) 1996-04-10

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EP91304405A Revoked EP0457589B1 (fr) 1990-05-17 1991-05-16 Compositions de combustible à caractéristiques de combustion augmentées

Country Status (5)

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EP (1) EP0457589B1 (fr)
JP (1) JP2931698B2 (fr)
AU (1) AU642242B2 (fr)
CA (1) CA2040818A1 (fr)
DE (1) DE69118583T2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5308365A (en) * 1993-08-31 1994-05-03 Arco Chemical Technology, L.P. Diesel fuel
US5669938A (en) * 1995-12-21 1997-09-23 Ethyl Corporation Emulsion diesel fuel composition with reduced emissions
WO2000053698A1 (fr) * 1999-03-09 2000-09-14 Idemitsu Kosan Co., Ltd. Additif pour gazole ou additif pour huile de graissage
US7029506B2 (en) * 2000-04-14 2006-04-18 Jordan Frederick L Organic cetane improver
WO2001079398A1 (fr) * 2000-04-14 2001-10-25 Oryxe Energy International, Inc. Agent d'amelioration du cetane organique
GB0021970D0 (en) 2000-09-07 2000-10-25 Octel Starreon Llc Diesel fuel stabiliser
US7141083B2 (en) 2001-03-22 2006-11-28 Oryxe Energy International, Inc. Method and composition for using organic, plant-derived, oil-extracted materials in resid fuel additives for reduced emissions
US7396450B2 (en) * 2003-09-18 2008-07-08 Afton Chemical Corporation Method of reducing amount of peroxides, reducing fuel sediments and enhancing fuel system elastomer durability, fuel stability and fuel color durability
US7615085B2 (en) 2003-11-04 2009-11-10 Afton Chemical Corporation Composition and method to reduce peroxides in middle distillate fuels containing oxygenates
US8292976B2 (en) * 2009-11-06 2012-10-23 Afton Chemical Corporation Diesel fuel additive for reducing emissions
GB2522621B (en) * 2014-01-29 2016-01-06 Rosario Rocco Tulino Formulation of a new diesel fuel suitable for diesel engines
WO2019089225A1 (fr) 2017-11-02 2019-05-09 Exxonmobil Research And Engineering Company Améliorant de cétane dans du mazout
EP4017945A1 (fr) * 2019-08-22 2022-06-29 ExxonMobil Research and Engineering Company Additifs pour carburants à faibles émissions de nox

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR821211A (fr) * 1937-03-04 1937-11-30 Perfectionnements aux combustibles pour moteurs

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US2031497A (en) * 1933-01-21 1936-02-18 Du Pont Fuel
GB697730A (en) * 1950-05-09 1953-09-30 Charles Walter Hodgson Improvements in and relating to liquid fuel catalysts and fuels resulting therefrom
FR1349941A (fr) * 1962-10-09 1964-01-24 Exxon Research Engineering Co Amélioration des caractéristiques de combustion des fuel oils
US4073626A (en) * 1974-04-18 1978-02-14 Ferrous Corporation Hydrocarbon fuel additive and process of improving hydrocarbon fuel combustion
US3957628A (en) * 1974-12-30 1976-05-18 Exxon Research And Engineering Company Removal of organic sulfur compounds from hydrocarbon feedstocks
US4328005A (en) * 1980-10-10 1982-05-04 Rockwell International Corporation Polynitro alkyl additives for liquid hydrocarbon motor fuels
AU574045B2 (en) * 1982-08-16 1988-06-30 Ethyl Corporation Diesel fuel composition
DE3233834A1 (de) * 1982-09-11 1984-03-15 Ruhrchemie Ag, 4200 Oberhausen Dieselkraftstoffe aus mitteldestillaten der kohlehydrierung
US4448587A (en) * 1983-03-28 1984-05-15 Ethyl Corporation Synergistic cetane improver
US4561862A (en) * 1985-04-08 1985-12-31 Olin Corporation Use of selected beta-nitroalkenes as cetane number boosters for diesel fuel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR821211A (fr) * 1937-03-04 1937-11-30 Perfectionnements aux combustibles pour moteurs

Also Published As

Publication number Publication date
JP2931698B2 (ja) 1999-08-09
JPH04227990A (ja) 1992-08-18
CA2040818A1 (fr) 1991-11-18
EP0457589A1 (fr) 1991-11-21
DE69118583D1 (de) 1996-05-15
AU7615691A (en) 1991-11-21
DE69118583T2 (de) 1996-09-19
AU642242B2 (en) 1993-10-14

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