EP0166096B1 - Combustibles pour moteurs - Google Patents

Combustibles pour moteurs Download PDF

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Publication number
EP0166096B1
EP0166096B1 EP19850104214 EP85104214A EP0166096B1 EP 0166096 B1 EP0166096 B1 EP 0166096B1 EP 19850104214 EP19850104214 EP 19850104214 EP 85104214 A EP85104214 A EP 85104214A EP 0166096 B1 EP0166096 B1 EP 0166096B1
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EP
European Patent Office
Prior art keywords
hydrocarbons
fuel
weight
methanol
mixture
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 - Lifetime
Application number
EP19850104214
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German (de)
English (en)
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EP0166096A1 (fr
Inventor
Heinrich Dr. Müller
Karl-Heinz Keim
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.)
DEA Mineraloel AG
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DEA Mineraloel AG
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Application filed by DEA Mineraloel AG filed Critical DEA Mineraloel AG
Priority to AT85104214T priority Critical patent/ATE58911T1/de
Priority to IN902/DEL/85A priority patent/IN169742B/en
Publication of EP0166096A1 publication Critical patent/EP0166096A1/fr
Priority to IN550/DEL/88A priority patent/IN169750B/en
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Publication of EP0166096B1 publication Critical patent/EP0166096B1/fr
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • the invention relates to fuels based on methanol and / or ethanol which contain additives to mixtures of C 5 / C 6 -, C 5 ⁇ C 7 hydrocarbons and gasoline and mixtures of C 4 hydrocarbons.
  • the hydrocarbons used can also be partially unsaturated or consist of unsaturated hydrocarbons (column 5, lines 28-34).
  • the additional components specified are n-pentane, isopentane and a C4 cut which contains up to 20% butenes.
  • a mixture of saturated C S hydrocarbons can also be used for the special case of fuel for aircraft engines in US Pat. No. 2,365,009, mixtures of ethanol with aliphatic C 3 -C, hydrocarbons are also described, the aliphatic hydrocarbons can be both saturated and unsaturated, and preferably isopentane (claim 8 and Table 1) is added as the hydrocarbon.
  • a process for producing a gaseous fuel mixture is described in GB-A-669,037 with 5-10% by volume of C 3 -C S hydrocarbons, C 2 ⁇ C 5 alcohols and 5-30% by volume of water.
  • FR-B-2,251,614 describes a method for producing and transporting an energy carrier. This consists of methanol and Cg-C 6 hydrocarbons dissolved therein, the proportion of C 3 hydrocarbons being 12.96% by weight. After transport, these can be wholly or partly expelled from the methanol.
  • the experts are aware of important fuel-specific disadvantages of the lower alcohols, e.g. the poor cold start behavior, the poor driving behavior at low outside temperatures, the inevitable miscibility with hydrocarbons, especially at low temperatures, and the wide explosion range.
  • the cold start problems are to be found in the low ignitability of the alcohols methanol and ethanol.
  • a measure of the ignitability is the vapor pressure of a fuel, which is measured according to the so-called Reid test at 38.0 ° C.
  • gasoline in the Reid test has a vapor pressure of 700 mbar, methanol, on the other hand, of 350 mbar.
  • methanol methanol
  • the vapor pressures of methanol and ethanol are so low that a gaseous, ignitable mixture is hardly possible.
  • the explosion limits of pure methanol in air are 6.75 to 36.7 vol.%, So that there is an explosive fuel-air mixture in the vehicle tanks between + 10 ° C and + 35 ° C. Additions of 6 ⁇ 9% by weight isopentane reduce the upper explosion limits to -7 ° C in summer and -20 ° C in winter. so that the security problems are largely eliminated.
  • Isopentane is also characterized by excellent solubility in both methanol and ethanol, especially at low temperatures.
  • the most favorable setting data for the vapor pressure of pure methanol turned out to be the upper vapor pressure values of the fuel standard DIN 51 600 with 700 mbar for summer and 900 mbar for winter fuel (Reid test).
  • isopentane (2-methylbutane) was therefore regarded as the optimal admixing component to date.
  • the vapor pressure is too high when pure methanol is used, despite lowering the isopentane content to 5 to 6% by weight, with undesirable outgassing of the isopentane occurring as a result, while in winter operation, despite an isopentane content up to 9% by weight at low Temperatures a vapor pressure drop occurs, which means that the cold start properties leave something to be desired in winter cold weather below -10 ° C.
  • a methanol fuel that contains saturated C 4 hydrocarbons and a mixture of saturated C S - Contains hydrocarbons with a proportion of> 12.3% by weight> C 5 hydrocarbons is disclosed in EP-A-0 118 805. (Release date: Jan 2, 1986).
  • the object of the present invention was to find fuels based on methanol and ethanol which provide better cold start behavior, better driving behavior, in particular at relatively high and relatively low outside temperatures, as is required in practical motor vehicle operation, with perfect solubility even in winter operation and less Ensure degassing in summer operation and, at the same time, ensure safe operation without an explosive mixture occurring in the fuel tank.
  • C 5 ⁇ C 7 hydrocarbons or gasoline such as those found in the refinery and primary chemicals production area, e.g. ethylene and gasoline / toluene (BT) plants, are eminently suitable, despite the different composition of individual hydrocarbons, the proportion of C 6 + C 7 hydrocarbons in the C 5 ⁇ C 7 mixture is> 12.3% by weight.
  • Examples of straight run, crack and catalytic crack cuts for the refinery sector may be mentioned, furthermore, for example, reformer cuts or Merox cuts.
  • the cuts claimed according to the invention are, however, not restricted to the cuts mentioned, since, as is known to the person skilled in the art, the fuel components according to the invention can also be obtained from other plants due to the different structure of the refining. It goes without saying that the hydrocarbons contained in the fuels according to the invention can also be obtained, including the C 4 hydrocarbons, in the form of a single technical cut.
  • the total amount of C 4 -hydrocarbons on the one hand and C-C 7 -hydrocarbons or gasoline on the other hand can be 0.1 to 25% by weight.
  • the ratio of C 4 hydrocarbons on the one hand to C 5 ⁇ C 7 hydrocarbons and petrol on the other hand can be 1: 500 to 3: 1.
  • a ratio of C 4 -hydrocarbons on the one hand and Cg-C 7 -hydrocarbons or gasoline on the other hand is preferred from 1: 1 to 1:20.
  • Suitable fractions of C 4 , C s , C 6 and C 7 mixtures are given as examples in the following analyzes, although the hydrocarbons contained in the fuels according to the invention cannot consist of such individual fractions but also of jointly cut fractions:
  • the methanol quality previously used for methanol-based fuels is methanol processed by distillation, so-called pure methanol (absolutely pure or refined methanol). It is known to the person skilled in the art that high demands are made with regard to the purity of this methanol quality, a correspondingly high level of operational effort being required, particularly in the distillation area. Since certain technical problems arise, especially with methanol fuel, e.g.
  • raw methanol contains up to approx. 5% by weight of water numerous impurities, e.g. Formaldehyde, methyl formate, formic acid, dimethyl sulfide, formaldehyde dimethyl acetal, iron pentacarbonyl and other carboxylic acids and their esters.
  • impurities e.g. Formaldehyde, methyl formate, formic acid, dimethyl sulfide, formaldehyde dimethyl acetal, iron pentacarbonyl and other carboxylic acids and their esters.
  • a tubular methanol can also be used which is not distilled but is topped off with removal of volatile impurities.
  • Fig. 1 the vapor pressure of a fuel made of pure or raw methanol and C 4 - / C 5 ⁇ C 7 hydrocarbons is plotted in mbar against the temperature range -30 to + 30 ° C for winter and summer.
  • Table 2 shows the compositions in% by weight, which are to be regarded as examples.
  • the fuels according to the invention include, in particular, compositions in which the total hydrocarbon quantity for summer and winter operation is as large as possible, since this means that no or only slight changes in the engine setting for winter and summer operation are required. This also applies to C 4 / C 5 ⁇ C 7 - as well as for CJ gasoline components or mixtures of hydrocarbons.
  • the preferred total amounts of hydrocarbons contained in the fuels according to the invention are 2-18 for C 4 -C 7 and 2-25% by weight for C 4 / gasoline.
  • Reid vapor pressures are 700 mbar for this summer fuel and 900 mbar for the winter fuel.
  • vapor pressures of the fuels according to the invention can vary within a certain range.
  • FIG. 6 This general behavior is shown in FIG. 6.
  • a single curve is shown in FIG. 7 for a mixture of 95.6% by weight of ethanol and C 5 / C 6 hydrocarbon additives. If the total amount of, for example, C 5 / C 6 hydrocarbons is kept constant, but if the ratio of C s to C s hydrocarbons varies, the result is a set of curves.
  • Fig. 2 is the vapor pressure of a fuel made of pure or raw methanol with the addition of petrol in mbar against the temperature range -30 ° C- + 30 ° C for winter and summer.
  • Table 3 shows the composition, in each case in% by weight:
  • Reid vapor pressures are 700 mbar for this summer fuel and 900 mbar for the winter fuel.
  • Figures 1 and 2 give surprising results for the person skilled in the art. (The common basis is the Reid steam pressure of 700 mbar for summer and 900 mbar for winter operation).
  • the vapor pressures of the fuels according to the invention shown in the curves in FIGS. 1 and 2 are summarized in Table 4 for -30 ° C. and + 30 ° C. They show that, for the person skilled in the art, the fuels according to the invention unpredictably ensure excellent vapor pressure behavior.
  • Table 7 summarizes the compositions of ethanol-based fuels according to the invention.
  • the ratio of C 5 -C 6 in this example is 1: 1. If the (preferred) concentration of C 5 / C 6 or C S -C 7 or OK has been determined in accordance with the concentration curve 6 or 7, then sufficient C 4 is added to obtain the desired pure steam pressure.
  • Reid vapor pressures of 700 mbar (summer) and 900 mbar (winter) are preferred as a comparison basis for the fuels according to the invention, but that other summer or winter vapor pressures can also be selected as the basis according to the invention, or that the vapor pressures of the fuels used in practical driving operation are variable in certain areas.
  • the fuels according to the invention can be additized, as is customary in the case of alcohol-based fuels.
  • Suitable corrosion inhibitors include e.g. those based on triazole, imidazole or benzoate.
  • Tricresyl phosphate e.g. Tricresyl phosphate, but also others, can be used.
  • emulsifiers such as glycols or their mono- and diether and others can be used.

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  • 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)

Claims (10)

1. Carburant à base de méthanol, renfermant éventuellement jusqu'à 15% en poids d'eau, caractérisé en ce qu'il contient un mélange d'hydrocarbures en C4 et un mélange d'hydrocarbures en Cs à C7,
a) la quantité totale d'hydrocarbures en C4 et en Cs à C7 dans ce carburant s'élevant à 0,1-18% en poids, et
b) le rapport des parties en poids d'hydrocarbures en C4 aux parties en poids d'hydrocarbures en C5 à C7 ayant une valeur de 1:500 à 3:1, et
c) la proportion d'hydrocarbures en C6+C7 dans le mélange C5/C6/C7 étant supérieure à 12,3% en poids.
2. Carburant à base de méthanol renfermant éventuellement jusqu'à 15% en poids d'eau, caractérisé en ce qu'il contient un mélange d'hydrocarbures en C4 et d'essence,
a) la quantité totale d'hydrocarbures en C4 et d'essence dans ce carburant s'élevant à 0,1-25% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 aux parties en poids d'essence ayant une valeur de 1:500 à 3:1.
3. Carburant à base d'éthanol renfermant éventuellement jusqu'à 25% en poids d'eau, caractérisé en ce qu'il contient un mélange d'hydrocarbures en C4 et un mélange d'hydrocarbures en C5/C6,
a) la quantité totale d'hydrocarbures en C4 et en C5/C6 dans ce carburant s'élevant à 0,1-15% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 aux parties en poids d'hydrocarbures en C5/C6 ayant une valeur de 1:500 à 3:1 et
c) la proportion d'hydrocarbures en C6 dans le mélange C5/C6 étant supérieure à 12,3% en poids.
4. Carburant à base d'éthanol renfermant éventuellement jusqu'à 25% en poids d'eau, caractérisé en ce qu'il contient un mélange d'hydrocarbures en C4 et un mélange d'hydrocarbures en C5―C7,
a) la quantité totale d'hydrocarbures en C4 et en C5―C7 dans ce carburant s'élevant à 0,1-18% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 aux parties en poids d'hydrocarbures en Cs-C7 ayant une valeur de 1:500 à 3:1 et
c) la proportion d'hydrocarbures en C6+C7 dans le mélange C5/C6/C7 étant supérieure à 12,3% en poids.
5. Carburant à base d'éthanol renfermant éventuellement jusqu'à 25% en poids d'eau, caractérisé en ce qu'il contient un mélange d'hydrocarbures en C4 et d'essence,
a) la quantité totale d'hydrocarbures en C4 et d'essence dans ce carburant s'élevant à 0,1-25% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 aux parties en poids d'essence ayant une valeur de 1:500 à 3:1.
6. Carburant suivant les revendications 1 à 5, caractérisé en ce qu'il est constitué d'un mélange d'au moins l'un des carburants révélés dans les revendications 1 à 5 et d'un second carburant à base de mèthanol, qui contient éventuellement jusqu'à 15% en poids d'eau et qui contient un mélange technique d'hydrocarbures en C4 et un mélange technique d'hydrocarbures en C5,
a) la quantité totale d'hydrocarbures en C4 et en C5 dans le second carburant ayant une valeur de 0,1 à 15% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 et Cs dans le second carburant ayant une valeur de 1:500 à 3:1.
7. Carburant suivant les revendications 1 à 6, caractérisé en ce qu'il est constitué d'un mélange d'au moins l'un des carburants révélés dans les revendications 1 à 6 et d'un second carburant à base d'éthanol, qui contient éventuellement jusqu'à 25% en poids d'eau et qui contient un mélange technique d'hydrocarbures en C4 et un mélange technique d'hydrocarbures en Cs,
a) la quantité totale d'hydrocarbures en C4 et Cs dans le second carburant s'élevant à 0,1-15% en poids et
b) le rapport des parties en poids d'hydrocarbures en C4 et en C5 dans le second carburant ayant une valeur de 1:500 à 3:1.
8. Carburant suivant les revendications 3 à 7, caractérisé en ce que l'éthanol utilisé est de l'éthanol contenant de l'eau.
9. Carburant suivant les revendications 1, 2 et 6 à 8, caractérisé en ce que le méthanol utilisé est du méthanol technique non distillé et/ou du méthanol technique étêté.
10. Carburant suivant les revendications 1 à 9, caractérisé en ce qu'il est constitué d'un mélange d'au moins deux des carburants révélés dans les revendications 1 à 9.
EP19850104214 1984-06-16 1985-04-06 Combustibles pour moteurs Expired - Lifetime EP0166096B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT85104214T ATE58911T1 (de) 1984-06-16 1985-04-06 Motor-kraftstoffe.
IN902/DEL/85A IN169742B (fr) 1984-06-16 1985-10-29
IN550/DEL/88A IN169750B (fr) 1984-06-16 1988-06-29

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP84106899 1984-06-16
EP84106899A EP0166006A1 (fr) 1984-06-16 1984-06-16 Combustible pour moteurs

Publications (2)

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EP0166096A1 EP0166096A1 (fr) 1986-01-02
EP0166096B1 true EP0166096B1 (fr) 1990-12-05

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ID=8191995

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Application Number Title Priority Date Filing Date
EP84106899A Withdrawn EP0166006A1 (fr) 1984-06-16 1984-06-16 Combustible pour moteurs
EP19850104214 Expired - Lifetime EP0166096B1 (fr) 1984-06-16 1985-04-06 Combustibles pour moteurs

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EP84106899A Withdrawn EP0166006A1 (fr) 1984-06-16 1984-06-16 Combustible pour moteurs

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DE (1) DE3580791D1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711985A1 (de) * 1987-04-09 1988-10-20 Union Rheinische Braunkohlen Verwendung von polyolethern zur verhinderung oder verminderung von ablagerungen in gemischaufbereitungssystemen
US6324827B1 (en) * 1997-07-01 2001-12-04 Bp Corporation North America Inc. Method of generating power in a dry low NOx combustion system
GB2333048B (en) * 1998-01-13 2002-03-20 Hugh F Collins A rejuvenating and/or cleaning agent
US6843813B1 (en) 2000-06-07 2005-01-18 Hugh Frederick Collins Rejuvenation and/or cleaning of catalysts
GB2433265A (en) * 2005-12-16 2007-06-20 Derek Lowe Low toxicity fuel
CN113088348A (zh) * 2021-04-09 2021-07-09 重庆邑丰新能源有限公司 一种工业用改性甲醇燃料及其制备方法
US12606757B2 (en) 2023-10-02 2026-04-21 Turn 3 Holdings LLC Alcohol based unleaded automotive racing fuel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5629920B2 (fr) * 1973-11-20 1981-07-11
JPS5416510A (en) * 1977-07-07 1979-02-07 Suzuki Motor Co Blended fuel for internal combustion engines
US4333739A (en) * 1979-10-23 1982-06-08 Neves Alan M Blended ethanol fuel

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Publication number Publication date
EP0166006A1 (fr) 1986-01-02
EP0166096A1 (fr) 1986-01-02
DE3580791D1 (de) 1991-01-17

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