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EP0127316B1 - Flammenluminositätsverbesserer für Methanol - Google Patents

Flammenluminositätsverbesserer für Methanol Download PDF

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Publication number
EP0127316B1
EP0127316B1 EP19840302782 EP84302782A EP0127316B1 EP 0127316 B1 EP0127316 B1 EP 0127316B1 EP 19840302782 EP19840302782 EP 19840302782 EP 84302782 A EP84302782 A EP 84302782A EP 0127316 B1 EP0127316 B1 EP 0127316B1
Authority
EP
European Patent Office
Prior art keywords
volume
composition
methanol
aromatic
fraction
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.)
Expired
Application number
EP19840302782
Other languages
English (en)
French (fr)
Other versions
EP0127316A2 (de
EP0127316A3 (en
Inventor
Jerome Panzer
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering 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 Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0127316A2 publication Critical patent/EP0127316A2/de
Publication of EP0127316A3 publication Critical patent/EP0127316A3/en
Application granted granted Critical
Publication of EP0127316B1 publication Critical patent/EP0127316B1/de
Expired legal-status Critical Current

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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

Definitions

  • This invention relates to a methanol fuel composition. More especially, the invention relates to a methanol fuel composition having improved flame luminosity.
  • methanol as a fuel for various needs, such as in spark ignition engines, is becoming more and more of interest because of the varying availability of different petroleum fuels and the change in costs of such fuels.
  • One of the problems that exists with the use of methanol is that it burns with a light blue flame that is almost invisible under normal light conditions such as daylight or a lighted room. Because it burns with such a nonluminous flame, the use of methanol presents a special safety hazard, especially when used as a fuel. Thus, a methanol spill could be very dangerous since its ignition might not be visible to people in the near vicinity.
  • Fuel compositions comprising aromatic and/or aliphatic hydrocarbons and up to 45 wt% of C 1 - 4 alcohol(s) are disclosed in DE - A-2 441 737.
  • the alcohol(s) are employed in admixture with water.
  • Fuel compositions of 9-45 wt% said alcohols, 90-50 wt% hydrocarbons and 1-5 wt% water are specifically referred to. Flame luminosity is not discussed in this reference.
  • a methanol fuel composition with improved flame luminosity which composition comprises at least 80 volume % of methanol, based on the total volume of the composition, and a petroleum hydrocarbon mixture of:
  • Another embodiment of this invention relates to the method of operating a spark ignition engine comprising the use of the methanol fuel composition of this invention to provide a luminous flame throughout its burning cycle.
  • the aromatic and saturate/olefin fractions which comprise the petroleum hydrocarbon mixture used in the composition of this invention can generally be obtained from any of the commonly available petroleum hydrocarbon mixtures or crude oils.
  • Such petroleum materials usually comprise a mixture of paraffinic, cycloparaffinic (naphthenes), olefinic and aromatic hydrocarbons.
  • the selected fractions are obtained from the starting petroleum materials by refining and separation techniques which are well known in the petroleum art including distillation, cracking, thermal diffusion, reforming etc.
  • the saturate/olefin hydrocarbon fraction of the petroleum hydrocarbon mixture will generally include paraffins, straight and branched chained, and cycloparaffins as well as some olefins.
  • the cycloparaffins comprise not only the monocyclic compounds, but the polycyclics and the alkyl substituted derivatives thereof. While this fraction will generally be derived from petroleum mixtures and crude oils where the saturate components, i.e., paraffins and cycloparaffins comprise the larger or predominant portion, nevertheless, there may be some olefinic components present.
  • the fractions derived from some operations, such as a cracking process can contain amounts of olefins which can vary up to about 20 vol.% or even higher.
  • Typical olefins will include the mono and diolefins such as cyclopentadiene.
  • the saturate/olefin hydrocarbon fraction will comprise at least 1 volume % and preferably at least 1.4 volume %, such volume based on the total volume of the composition.
  • the aromatic hydrocarbon fraction will comprise at least 2% by volume and preferably at least 2.5% by volume, based on the total volume of the composition and will contain a number of different compounds.
  • This aromatic hydrocarbon fraction will include at least 1 volume % based on the total volume of the composition of a mixture of aromatic hydrocarbons which distil substantially uniformly over a wide boiling range having an initial boiling point of less than 115°C (240°F) and a final boiling point of greater than (190°C (375°F).
  • distilling substantially uniformly it is meant that this portion of the aromatic fraction will distil at a fairly uniform rate, i.e., a rate such that the distillation curve (temperature vs.
  • this aromatic mixture will comprise a number of different hydrocarbons which distil at different temperatures throughout the desired temperature range and are present in sufficient quantities to provide distillation which is substantially uniform, i.e. the distillation rate is generally smooth or even over the temperature range. What in effect is needed to obtain a generally uniform distillation is a small amount, usually less than about 10 volume %, of a large number of different compounds.
  • Typical compounds found in the aromatic fraction are the alkylbenzenes such as toluene, the xylenes and p-cymene, the polycyclic aromatics such as naphthalenes, biphenyl, acenaphthene, fluorenes, phenanthrenes, mononaphthene benzenes and dinaphthene benzenes. It is understood that branched or substituted ring components are also included in the defined aromatic fraction.
  • both the aromatic and saturate/olefin fractions will comprise a mixture of compounds containing 5 to 12 carbon atoms per molecule.
  • Each fraction will generally contain a variety of branched substituents and may contain small amounts of sulfur and nitrogen content.
  • the procedure "Hydrocarbon Types by FIA,” ASTM D-1319 is used.
  • a further description of petroleum hydrocarbon fractions of this type and typical compounds in such petroleum compositions is given in Kirk-Othmer, "Encyclopedia of Chemical Technology,” 2nd Edition, Vol. 14, pp. 845-855, 1967.
  • the petroleum hydrocarbon mixture comprising the aromatic and saturate/olefin fractions as defined herein will generally comprise at least 3 volume % and preferably at least 4 volume % of the total composition; however greater amounts can be used with cost efficiency being a prime factor in determining the upper limit for the amounts to be used.
  • the important thing about this added petroleum hydrocarbon mixture is that it form an azeotropic mixture which includes all of the methanol. While the azeotrope could comprise part of the petroleum hydrocarbon mixture itself, it must include all of the methanol. This makes it possible for the petroleum mixture or luminosity component to be co-distilled with the methanol and to impart luminosity as long as a flame exists.
  • the select wide boiling aromatic component which makes up part of the aromatic fraction must distil substantially uniformly over a range having an initial boiling point of less than 115°C 240°F and a final boiling point of greater than 190°C (375°F).
  • the petroleum hydrocarbon mixture i.e. combined aromatic and saturate/olefin fractions must have an initial boiling point of less than 65°C (150°F) and a final boiling point of greater than 190°C (375°F).
  • ASTM D-86 is a procedure that is generally followed.
  • composition of this invention is relatively water insensitive to small amounts of water.
  • hydrocarbon components such as gasoline
  • problems can develop when water is present.
  • problems such as phase separation or increased volatility can develop in such compositions when fairly small amounts of water are present.
  • the composition of this invention has been found to be water insensitive even when amounts of water of up to about 3 volume % are present and still retains its ability to maintain flame luminosity.
  • flame luminosity as used throughout this application is meant that the flame is clearly visible and distinguishable.
  • composition of this invention may be used in several applications but is particularly useful as a fuel for operating a spark ignition engine.
  • a primer such as dimethyl ether is a particularly useful additive to the fuel composition of this invention in certain applications since it provides good volatility at low temperatures to help in cold starting.
  • the amount of primer will depend on ambient temperatures and the particular engine being used. Typically about 2 to about 7 volume % based on the total volume of the composition will be used.
  • minor amounts of other additives generally used with fuel compositions of this type may be included in the composition of this invention, e.g. corrosion and rust inhibitors, antioxidants, etc.
  • the total amount of other additives, i.e., besides the petroleum hydrocarbon mixture and primer will be less than about 1 volume % based on the total volume of the composition.
  • a fuel composition comprising methanol and optionally dimethyl ether primer was tested for flame luminosity after adding a number of petroleum hydrocarbon mixtures with the following results as shown in the table below.
  • composition containing the amounts and the saturate/olefin and aromatic fractions in accordance with this invention as shown by the use of the mixed hydroformate or combinations of toluene and light cat naphtha provide flame luminosity over 100% of the entire burning cycle.
  • other additive mixtures did not give the desired flame luminosity at least not over the entire burning cycle.
  • the compositions in accordance with this invention were found to hold more than 3 volume % water without phase separation or a change in volatility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

1. Methanolbrennstoffzusammensetzung mit verbesserter Flammenleuchtkraft, die mindestens 80 Vol.% Methanol bezogen auf das Gesamtvolumen der Zusammensetzung und eine Petrolkohlenwasserstoffmischung aus
(a) mindestens 2 Vol.% einer aromatischen Kohlenwasserstofffraktion, bezogen. auf das Gesamtvolumen der Zusammensetzung, wobei die Fraktion bezogen auf das Gesamtvolumen der Zusammensetzung mindestens 1 Vol.% aromatische Kohlenwasserstoffe einschließt, die in einem breiten Siedebereich mit einem Anfangssiedepunkt von weniger als 115°C (240°F) und einem Endsiedepunkt von mehr als 190°C (375°F) im wesentlichen einheitlich destillieren, und
(b) mindestens 1 Vol.% einer Fraktion gesättigter/olefinischer Kohlenwasserstoffe, bezogen auf das Gesamtvolumen der Zusammensetzung,

enthält, wobei die Kohlenwasserstoffmischung einen Anfangssiedepunkt von weniger als 65°C (150°F) und einen Endsiedepunkt von mehr als 190°C (375°F) aufweist und sich mit dem Methanol unter Bildung einer das gesamte Methanol einschließenden azeotropen Mischung kombiniert, wobei die Zusammensetzung in der Lage ist, während ihrer Brenndauer mit einer leuchtenden Flamme zu brennen und bezogen auf das Gesamtvolumen der Zusammensetzung zumindest 3 Vol.% Wasser ohne Phasentrennung oder eine wesentlichen Veränderung der Flüchtigkeit zu tolerieren.
2. Zusammenstezung nach Anspruch 1, in der eine wirksame Zündmenge Dimethylether vorhanden ist.
3. Zusammensetzung nach Anspruch 1 oder 2, in der zumindest 2,5 Vol.% der aromatischen Fraktion vorhanden sind.
4. Zusammensetzung nach einem der vorangehenden Ansprüche, in der zumindest 1,4 Vol.% der gesättigten/olefinischen Fraktion vorhanden sind.
5. Zusammensetzung nach einem der vorangehenden Ansprüche, in der sowohl die aromatische als auch die gesättigte/olefinische Fraktion eine Mischung aus Verbindungen umfassen, welche 5 bis 12 Kohlenstoffatome pro Molekül enthalten.
6. Zusammensetzung nach einem der vorangehenden Ansprüche, in der die die aromatische und die gesättigte/olefinische Fraktion umfassende Petrolkohlenwasserstoffmischung zumindest 3 Vol.%, bevorzugt zumindest 4 Vol.%, der gesamten Zusammensetzung ausmacht.
7. Verfahren zum Betrieb eines Zündermotors, bei dem die Zusammensetzung nach einem der vorangehenden Ansprüche als Brennstoff verwendet wird, um eine leuchtende Flamme während der Brenndauer zu liefern.
EP19840302782 1983-04-29 1984-04-25 Flammenluminositätsverbesserer für Methanol Expired EP0127316B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48973583A 1983-04-29 1983-04-29
US489735 1983-04-29

Publications (3)

Publication Number Publication Date
EP0127316A2 EP0127316A2 (de) 1984-12-05
EP0127316A3 EP0127316A3 (en) 1985-12-27
EP0127316B1 true EP0127316B1 (de) 1988-10-05

Family

ID=23945064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840302782 Expired EP0127316B1 (de) 1983-04-29 1984-04-25 Flammenluminositätsverbesserer für Methanol

Country Status (8)

Country Link
EP (1) EP0127316B1 (de)
JP (1) JPS59207987A (de)
AU (1) AU577528B2 (de)
CA (1) CA1255503A (de)
DE (1) DE3474459D1 (de)
DK (1) DK214584A (de)
NO (1) NO841655L (de)
NZ (1) NZ207977A (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4932979A (en) * 1987-08-27 1990-06-12 Xl, Inc. Methanol fuel mixture
WO1990003421A1 (en) * 1988-09-21 1990-04-05 Xl, Inc. Methanol fuel mixture
US5147413A (en) * 1989-07-20 1992-09-15 The Standard Oil Company Methanol fuel containing flame luminosity agent
US5266080A (en) * 1989-10-11 1993-11-30 The Standard Oil Company Methanol fuel containing flame luminosity agent
JPH0739582B2 (ja) * 1991-11-22 1995-05-01 吉彦 篠尾 低公害燃料組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2441737A1 (de) * 1974-08-30 1976-03-11 Gerhard Goldmann Fluessige treibstoffkombination auf basis von kohlenwasserstoffen mit vermindertem gehalt an schaedlichen verbrennungsrueckstaenden sowie verfahren zu deren herstellung

Also Published As

Publication number Publication date
NZ207977A (en) 1986-09-10
NO841655L (no) 1984-10-30
EP0127316A2 (de) 1984-12-05
EP0127316A3 (en) 1985-12-27
CA1255503A (en) 1989-06-13
DE3474459D1 (en) 1988-11-10
JPS59207987A (ja) 1984-11-26
AU2747484A (en) 1984-11-01
DK214584D0 (da) 1984-04-27
DK214584A (da) 1984-10-30
AU577528B2 (en) 1988-09-29

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