EP2449064A1 - Carburants combustibles constitués d'un mélange de butanols - Google Patents

Carburants combustibles constitués d'un mélange de butanols

Info

Publication number
EP2449064A1
EP2449064A1 EP10749683A EP10749683A EP2449064A1 EP 2449064 A1 EP2449064 A1 EP 2449064A1 EP 10749683 A EP10749683 A EP 10749683A EP 10749683 A EP10749683 A EP 10749683A EP 2449064 A1 EP2449064 A1 EP 2449064A1
Authority
EP
European Patent Office
Prior art keywords
butanol
fuel
vol
fuel composition
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10749683A
Other languages
German (de)
English (en)
Inventor
Wei Xu
Stephan Ralf Vogel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Arabian Oil Co
Aramco Services Co
Original Assignee
Saudi Arabian Oil Co
Aramco Services Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Arabian Oil Co, Aramco Services Co filed Critical Saudi Arabian Oil Co
Publication of EP2449064A1 publication Critical patent/EP2449064A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number

Definitions

  • the present invention relates to a fuel component and composition and an octane enhancer, including the method of creating the same.
  • Internal combustion engines are commonly used on mobile platforms, in remote areas or in lawn and garden tools. There are various types of internal combustion engines. Spark type engines compress volatile fuels, such as gasoline, before ignition. Compression type engines take in air and compress it to generate the heat necessary to ignite the fuel, such as diesel.
  • the ethanol is blended into gasoline in various quantities, normally at 10%, which typically results in a higher octane rating than regular gasoline.
  • E-85 fuel contains 85% ethanol and 15% gasoline and M-85 has 85% methanol and 15% gasoline.
  • many of the elastomer ic engine seals, hoses and gasket components were designed only for gasoline or diesel and deteriorated with the use of ethanol.
  • the engines had to be equipped with fluorinated elastomers to run ethanol-based fuels.
  • the ethanol is often created through fermentation processes from grain.
  • Bio-fuels often contain mixed alcohols together with other oxygenate compounds.
  • Long chain alcohols are often used together with amines/anilines as inhibitors to prevent metal corrosion and rubber/plastics swellings caused by the ethanol fuels. These long chain alcohols, such as dodecanol, can also be used as emulsifying agents. Mixed low cost methanol, ethanol were used together with long chain alcohols to form alcohol blended diesels or used as emulsifying diesel adjustors. However, long chain alcohols are relatively expensive to produce. The methanol-based and ethanol-based diesel also suffer from the drawback that they need other additives, such as long chain alcohol, alkyl esters and fatty acids to maintain a minimum Cetane number above 40 and to assure the diesel burns efficiently.
  • MTBE is itself a pollutant, having an objectionable and strong odor and taste and having been classified as a potential human carcinogen.
  • MTBE leakage from underground storage tanks has created a demand for an alternative product, particularly as MTBE is soluble in water (42 g/L @ 25°C) and is low in biodegradability thereby polluting ground water.
  • U.S. states, including California, are phasing out the use of MTBE.
  • MMT Methylcyclopentadienyl Manganese Tricarbonyl
  • fuel additives and fuel compositions are provided as embodiments of the present invention.
  • a fuel composition that is environmentally friendly and has comparable performance properties to ethanol-based or MTBE-based fuels is provided.
  • the fuel composition includes a fuel component and a fuel additive.
  • the fuel composition consists essentially of a fuel component and a fuel additive.
  • the fuel component being present in an amount sufficient to provide adequate BTU content for use in combustion or compression engines.
  • the fuel additive includes at least two isomers of butanols and is present in an amount sufficient to improve an octane rating for the fuel composition.
  • the neat fuel composition includes a mixed butanol fuel.
  • the neat fuel composition consists essentially of a mixed butanol fuel.
  • the current invention includes compositions of at least two of 2-butanol, iso-butanol or tert-butanol, in combination with or as a fuel for use in combustion or compression engines.
  • 2-butanol, iso-butanol and tert-butanol are used.
  • the at least two or more of 2-butanol, iso-butanol or tert-butanol are referred to as "mixed butanols" hereafter.
  • Mixed butanols are useful as a combustible neat fuel or as an oxygenate fuel constituent in gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil or other similarly hydrocarbon based fuel stock to create a butanol enhanced fuel.
  • the combustible neat fuel and the butanol enhanced fuel demonstrate numerous benefits in comparison to gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker o ⁇ or other similarly hydrocarbon based fuels without the mixed butanols. These benefits include increased demonstrated combustion efficiency, reduced emissions of harmful gases and particulate matter.
  • the butanol enhanced fuel and the combustible neat fuel show improved BTU content on a volumetric basis when compared to similar fuels containing substantial amounts of methanol or ethanol.
  • mixed butanols act as an octane enhancer as a replacement to tetra-ethyl-lead, MTBE, methanol, ethanol, MMT and other octane boosters.
  • Mixed butanols do not suffer from the drawbacks associated with these other octane boosters.
  • the butanol enhanced fuel mixed butanols demonstrate low and stable Reid vapor pressure blending characteristics. Given the reduced corrosiveness of mixed butanols as compared to methanol/ethanol, the combustible neat fuel or the butanol enhanced fuel can be safely stored in existing storage and transportation facilities and can be used in modern engines without engine modifications.
  • An added benefit is the low toxicity of the mixed butanols and the relative biodegradability which makes the mixed butanols a clear choice for environmental reasons to replace other octane boosters.
  • Butanol isomers due to their different structures, have somewhat different physical properties. Isobutanol, 2-butanol, and n-butanol have only limited solubility in water, as contrasted to methanol, ethanol, and propanol, which are fully miscible with water. Therefore, the mixed butanol of the current invention provides environmental advantages over the use of C1-C3 alcohols. 2-butanol is particularly preferred as a predominant portion of the mixed butanols.
  • Butanols of the current invention can be derived from various sources, including reaction to derive butanols from fossil fuels or through fermentation of biomass from bacteria.
  • the current invention encompasses any combination of butanol isomers to create the mixed butanols.
  • One preferred embodiment includes the mixed butanols being 5-95 volume % 2-butanol and 5-95 volume % tert-butanol; or alternatively, being 40-60 volume % 2- butanol and 40-60 volume % tert-butanol.
  • This mixed butanol is preferably 1-60 vol % of the butanol enhanced fuel.
  • the presence of any substantial amounts of methanol, ethanol, and propanol in the combustible neat fuel and the butanol enhanced fuel is also possible.
  • the mixed butanols used in embodiments of the present invention can include a variety of butanols.
  • the mixed butanols includes n- butanol or bio-butanol.
  • the mixed butanols excludes n-butanol or bio-butanol.
  • the fuel compositions described herein exclude the use of tetraethyllead, MTBE, methanol, ethanol, or MMT.
  • the fuel compositions of the present invention have physical properties that are comparable to fuel compositions containing alcohol-based, such as ethanol-based, octane enhancers, but without many of the disadvantages associated with such fuel compositions.
  • the physical properties that are important to fuel compositions include RON values, BTU values, RVP values, MON values, cetane index values, heat of combustion, cloud point values, pour point values, smoke point values, and the like.
  • the fuel compositions of the present invention exclude the use of non-butanol alcohols.
  • the fuel compositions of the present invention exclude the use of methanol, ethanol, or propanol. However, these alcohols can be blended with the mixed butanol based fuels at any ratios.
  • the mixed butanols are an effective replacement for tetra-ethyl-lead, MTBE and MMT.
  • MTBE tetra-ethyl-lead
  • MMT is still used in some fuel blends in the world, a preferred embodiment of the current invention includes an absence of MMT.
  • lower ketones such as acetone
  • the current invention is practiced substantially in the absence of such lower ketones.
  • Another advantage of the invention and the exclusion of the use of methanol and ethanol is the ability to also exclude long chain alkyl esters and fatty acids that are often used with methanol/ethanol to maintain a minimum Cetane number of about 40 and to assure that dies el bums efficiently.
  • the fuel composition includes a fuel component and a fuel additive.
  • the fuel component being present in an amount sufficient to provide adequate BTU content for use in combustion or compression engines.
  • the fuel additive includes a butanol and is present in an amount sufficient to improve an octane rating for the fuel composition.
  • the butanol consists essentially of 2-butanol and tert- butanol, or combinations thereof.
  • the butanol excludes n-butanol.
  • the butanol included in the fuel additive includes n-butanol.
  • the butanol includes 2-butanol, iso-butanol, tert-butanol, or combinations thereof.
  • the butanol includes 2-butanol and tert-butanol.
  • the 2-butanol is present in a range of about 5 vol. % to about 95 vol. % and the tert-butanol is present in a range of about 5 vol. % to about 95 vol. %.
  • the 2-butanol is present in a range of about 40 vol. % to about 60 vol.
  • tert-butanol is present in a range of about 40 vol. % to about 60 vol. %.
  • Other suitable types of mixed butanols and amounts of butanols will be apparent to those of skill in the art and are to be considered within the scope of the present invention.
  • the fuel compositions of the present invention have physical properties that are comparable to fuel compositions containing ethanol-based, or MTBE based, octane enhancers, but without many of the disadvantages associated with such fuel compositions.
  • the physical properties that are important to fuel compositions include RON values, BTU values, RVP values, MON values, cetane index values, heat of combustion, cloud point values, pour point values, smoke point values, and the like.
  • the fuel compositions of the present invention exclude the use of non-butanol alcohols.
  • the fuel compositions of the present invention exclude the use of methanol, ethanol, or propanol.
  • the fuel compositions described herein exclude the use of tetraethyllead, MTBE, methanol, ethanol, or MMT.
  • the octane number does not correspond to the concentration of any one constituent in the fuel, but rather to the pre-ignition properties of the fuel as compared with standard fuel mixtures.
  • the octane rating is a measure of the autoignition resistance of gasoline (petrol) and other fuels used in spark-ignition internal combustion engines.
  • Octane is measured relative to a mixture of isooctane (2,2,4-trimethylpentane, an isomer of octane) and n- heptane.
  • an 87 -octane gasoline has the same knock resistance as a mixture of 87 vol-% isooctane and 13 vol-% n-heptane.
  • RON Research Octane Number
  • RON is determined by running the fuel through a specific test engine with a variable compression ratio under controlled conditions, and comparing these results with those for mixtures of isooctane and n-heptane.
  • the "headline" octane that is shown on the pump is the RON.
  • Activation energy is the amount of energy necessary to start a chemical reaction. Since higher octane fuels have higher activation energies, it is less likely that a given compression will cause knocking. Knocking can damage an engine. Lower-octane gas (e.g., 87-octane gasoline) can handle the least amount of compression before igniting.
  • Engine power is a function of the fuel as well as the engine design and is related to octane ratings of the fuel. Power is limited by the maximum amount of fuel-air mixture that can be forced, into the combustion chamber. At partial load, only a small fraction of the total available power is produced because the manifold is operating at pressures far below atmospheric. In this case, the octane requirement is far lower than what is available. It is only when the throttle is opened fully and the manifold pressure approaches to atmospheric (or higher in the case of supercharged or turbocharged engines) that the full octane requirement is achieved.
  • Engines perform best when using fuel with the octane rating they were designed for. There can possibly be a minimal increase in performance by using a fuel with a different octane rating.
  • the most common type of octane rating is the Research Octane Number (RON).
  • RON is determined by running a fuel in a test engine with a variable compression ratio under controlled conditions, and comparing the results with those for mixtures of iso-octane and n-heptane.
  • the fuel compositions of the present invention have RON values ranging from between about 85 and to about 1 10.
  • the fuel compositions of the present invention have BTU values are ranging from between about 105,000 BTU/gallon and to about 120,000 BTU/gallon.
  • the fuel compositions of the present invention have a RVP ranging from about 0.2 psi to about 20 psi.
  • MON Motor Octane Number
  • aviation lean octane rating is generally a better measure of how fuel behaves when under load as it is done at 900 rpm instead of the 600 rpm of the RON.
  • MON testing typically uses a similar test engine to that used in RON testing, but with a preheated fuel mixture, a higher engine speed, and variable ignition timing to further stress the fuel's knock resistance.
  • the MON of a modern gasoline will be about 8 to 10 points lower than the RON.
  • fuel specifications require both a minimum RON and a minimum MON.
  • the fuel compositions of the present invention have MON values ranging from about 75 to about 100.
  • Cetane number or CN is a measurement of the combustion quality of diesel fuel during compression ignition. Cetane number is a measure of a fuel's ignition delay; the time period between the start of injection and start of combustion (ignition) of the fuel. In a particular diesel engine, higher cetane fuels will generally have shorter ignition delay periods than lower cetane fuels. In an aspect, the fuel compositions of the present invention have cetane index values ranging from about 48 to about 55.
  • the energy content (also referred to as heating value) of diesel fuel is its heat of combustion; the heat released when a known quantity of fuel is burned under specific conditions.
  • the fuel compositions of the present invention have heat of combustion values ranging from about 1 18,000 BTU/gal to about 130,000 BTU/gal.
  • the cloud point of a fuel is the temperature at which dissolved paraffin is no longer completely soluble, precipitating as a second phase giving the fuel a cloudy appearance.
  • the fuel compositions of the present invention have cloud point values ranging from about -40 0 C to about 5°C; or alternatively, ranging from about 4.5°C to about 5.75°C.
  • the fuel's pour point is a temperature below the fuel's cloud point. Fuel stops flowing below the pour point.
  • the fuel compositions of the present invention have pour point values ranging from about 5-12°C below the cloud point.
  • the fuel compositions of the present invention have smoke point values ranging from about 10 mm to about 25 mm.
  • Smoke point is defined as the flame height immediately prior to the flame emitting smoke.
  • Smoke point has been recognized as a measure of a fuel to form soot and has been used to judge the quality of various liquid fuels.
  • the fuel composition includes a fuel component.
  • the fuel component includes gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, or combinations thereof.
  • Other types of fuels can be used in embodiments of the present invention will be apparent to those of skill in the art and are to be considered within the scope of the present invention.
  • the fuel component is present in a range of about 40 vol. % to about 99 vol. % and the fuel additive is present in a range of about 1 vol. % to about 60 vol. %; or alternatively, the fuel component is present in a range of about 80 vol. % to about 99 vol. % and the fuel additive is present in a range of about 1 vol. % to about 20 vol. %.
  • the amounts of each component can vary depending upon the desired physical properties of the resulting fuel composition. Other suitable amounts of each component will be apparent to those of skill in the art and are to be considered within the scope of the present invention.
  • the neat fuel composition comprises a mixed butanol fuel.
  • the mixed butanol fuel includes 2-butanol, iso-butanol, tert-butanol, or combinations thereof.
  • the mixed butanol fuel consisting essentially of only 2-butanol, iso-butanol, tert-butanol, or combinations thereof.
  • the mixed butanol fuel excludes n-butanol.
  • a method of preparing a fuel composition for use in combustion or compression engines is also provided.
  • a mixed butanol composition is combined with a fuel component.
  • the mixed butanol composition includes 2-butanol, iso-butanol, tert-butanol, or combinations thereof and is present in an amount sufficient to improve an octane rating for the fuel composition.
  • the fuel component includes gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, or combinations thereof.
  • the fuel component is present in an amount sufficient to provide adequate BTU content for use in combustion or compression engines.
  • the fuel component is present in a range of about 40 vol. % to about 99 vol.
  • the fuel additive is present in a range of about 1 vol. % to about 60 vol. %; or alternatively, in a range of about 80 vol. % to about 99 vol. % and the fuel additive is present in a range of about 1 vol. % to about 20 vol. %.
  • the composition's RON values are between 85 and 110; or alternatively, between 67.4 and 101.1.
  • the composition's BTU values are between 105,000 BTU/gallon and 120,000 BTU/gallon.
  • a method of using a mixed butanols composition as combustible neat fuels and/or oxygenate fuel constituents in gasoline, diesel, jet fuel, aviation gasoline, heating oil, bunker oil, or combinations thereof is provided.
  • the mixed butanols composition is comprised of at least two of n-butanol, 2-butanol, iso-butanol and tert-butanol, preferably 2-butanol, iso-butanol, and tert-butanol.
  • the mixed butanol fuel includes 2-butanol, iso-butanol, tert-butanol, or combinations thereof.
  • the mixed butanols composition consisting essentially of only 2-butanol, iso-butanol, tert- butanol, or combinations thereof.
  • the mixed butanols composition excludes n- butanol.
  • the current invention creates an advantage due to the high value of BTU/gallon of the mixed butanols.
  • Methanol contains about 57,250 Btu's/gallon and ethanol contains about 76,330 Btu's/gallon while gasoline contains about 116,100 Btu's/gal.
  • the mixed butanols are closer to the Btu/gallon value of gasoline.
  • Table 1 includes a list of the test methods used to test the fuels made in accordance with embodiments of the present invention. The test results are shown in Table 2.
  • Diesel used for the experiments was obtained from one Aramco refinery without any other additives. Diesel and butanols were blended as listed in Table 5 which contains 10% butanols and 90% diesel fuel. The test results are listed in Table 6.
  • Runs 21-26 demonstrate that there are no significant negative effects (cloud point, smoke point, BTU) introduced when mixed butanols are added to the diesel at 10% level. Both Cetane and RVP are slightly reduced.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne une composition de carburant comprenant un mélange de butanols tels que, par exemple, 2-butanol, iso-butanol et tert-butanol, de préférence 2-butanol et tert-butanol. Elle concerne également des méthodes de préparation et d'utilisation de la composition à base de mélange de butanols en tant que carburants purs combustibles et/ou constituants de carburant oxygéné présents dans l'essence, le diesel, le carburant aviation, l'essence aviation, l'huile de chauffage, le combustible de soute et analogues.
EP10749683A 2009-07-01 2010-06-29 Carburants combustibles constitués d'un mélange de butanols Withdrawn EP2449064A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US22237409P 2009-07-01 2009-07-01
US12/824,432 US20110023355A1 (en) 2009-07-01 2010-06-28 Combustible Mixed Butanol Fuels
PCT/IB2010/001760 WO2011001285A1 (fr) 2009-07-01 2010-06-29 Carburants combustibles constitués d'un mélange de butanols

Publications (1)

Publication Number Publication Date
EP2449064A1 true EP2449064A1 (fr) 2012-05-09

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP10749683A Withdrawn EP2449064A1 (fr) 2009-07-01 2010-06-29 Carburants combustibles constitués d'un mélange de butanols

Country Status (5)

Country Link
US (1) US20110023355A1 (fr)
EP (1) EP2449064A1 (fr)
JP (1) JP2012532241A (fr)
CA (1) CA2767100A1 (fr)
WO (1) WO2011001285A1 (fr)

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JP5699032B2 (ja) * 2011-05-02 2015-04-08 出光興産株式会社 ガソリン組成物
JP5699033B2 (ja) * 2011-05-02 2015-04-08 出光興産株式会社 ガソリン組成物
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CN104039435B (zh) 2011-12-05 2016-03-02 沙特阿拉伯石油公司 集成亲水膜的烯烃水合方法
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US9120991B2 (en) * 2013-10-31 2015-09-01 Shell Oil Company High octane unleaded aviation gasoline
KR101869762B1 (ko) * 2017-12-18 2018-06-21 한국석유관리원 연료 복합 첨가제
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Also Published As

Publication number Publication date
US20110023355A1 (en) 2011-02-03
WO2011001285A1 (fr) 2011-01-06
JP2012532241A (ja) 2012-12-13
CA2767100A1 (fr) 2011-01-06

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