CN101981165B - Use of alcohols in fuels for spark ignition engines - Google Patents

Use of alcohols in fuels for spark ignition engines Download PDF

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Publication number
CN101981165B
CN101981165B CN200980104801.XA CN200980104801A CN101981165B CN 101981165 B CN101981165 B CN 101981165B CN 200980104801 A CN200980104801 A CN 200980104801A CN 101981165 B CN101981165 B CN 101981165B
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volume
fuel
alcohol
mixture
purposes
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CN101981165A (en
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M·库贝尔卡
P·普拉策克
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Butamax Advanced Biofuels LLC
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Butamax Advanced Biofuels LLC
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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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

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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)
  • Output Control And Ontrol Of Special Type Engine (AREA)

Abstract

The use of at least one C4 alcohol to increase the vapour pressure of a fuel for spark-ignition engines comprising base fuel and ethanol in which use the at least one C4 alcohol is added to a fuel comprising base fuel and ethanol to produce a resultant fuel mixture comprising 15-50 % by volume of base fuel, 15-65 % by volume of ethanol and 15 to 50 % C4 alcohol. The resultant fuel mixture exhibits an adequately high vapour pressure, for example, which meets the specification, and also exhibits a good start behaviour even at winter temperatures.

Description

The purposes of alcohol in fuels for spark ignition engines
The present invention relates to the purposes of alcohol in fuels for spark ignition engines, and relate to the preparation of fuels for spark ignition engines.Except ethanol, these fuel also comprise C 4alcohol.
Fuels for spark ignition engines is the motor spirit that is applicable to spark ignition engine.They comprise the mixture of the different hydrocarbon with different boiling conventionally, and the described boiling point under normal atmosphere is conventionally in the scope of 26 DEG C to 210 DEG C.But this scope is not clearly predetermined, and can be depending on the actual composition of hydrocarbon, additive and other component, and depend on envrionment conditions.Conventionally, the hydrocarbon component of fuel comprises C 4-C 10hydrocarbon.
The requirement that must reach in spark ignition preparation of fuel is many-sided.They are results of regulation, distribution chain and their application in engine.In addition to these, prepare in addition actual conditions and different driven Designs, this need to be divided into spark ignition fuel different types.In Germany, implement minimum requirements according to decree with the form of DIN Standards (DIN standard).In service station, they must be identified with suitable mark.The Fuel Quality Decree (fuel mass decree) proposing in 1993 and upgrade 2004 and 2006 only allows to meet the fuel of all DIN Standard EN228 requirements now.In the U.S., apply corresponding specification according to ASTM 4814.
In order to reach best transmission condition, fuel should meet the various different requirements of vehicle.Under particular case, this refers to: experiencing after cold long night, engine should be easy to start as summer; That is to say, as stopped the engine restart of rear obvious heating between of short duration.And in the time of idle running, engine should not stop working; And under high capacity, should not become unstable.Even under disadvantageous condition, interference resistates does not have in inlet system, combustion chamber or oil groove yet.
Fuel should adapt to these different and partly requirements of contradiction in some way, so that trouble free, reliable and mutually beneficial interaction become possibility.Therefore, German brand manufacturer is blended into the material that is called as " mineral oil alternative compositions " of limited proportion in basic fuel as the chemically reactive substance of alcohol and ether and maximum 0.5 % by weight.
To the fuel for being called as propellant combination vehicle, specify the specific requirement of the alcohol content with 0 volume % to 85 volume % ethanol.For the fuel with 70 volume % to 85 volume % ethanol that is called as E85, the vapour pressure of cold start-up mode is especially crucial.Have high-content alcohol as the fuel of ethanol or different alcohol mixtures be known.Patent application HK 106 428, US2006/0137243, US 2004/0107634 and US 2004/123518 have mentioned these by way of example.
Also known, make " the super white gasoline " of typical refining or research octane number (RON) (being also called as RON) be summer of 95 or winter quality gasoline mix with the bio-ethanol of 70 volume % or 85 volume %.According to draft specifies CWA 15293 and 51625 (in the October, 2007 of Draft Standard E DIN of in May, 2005 CEN Workshop Agreement, Beuth Verlag) suggestion, the minimum vapour pressure in summer is 35kPa (A level), and the minimum vapour pressure in winter is 50kPa (B level).According to the vapour pressure of the super white gasoline in basis or Fuel Petroleum, the vapour pressure of gasoline/alcohol mixture may not meet draft specifies.In these cases, the alcohol concn in mixture must be lowered, this is worthless.
Therefore, the object of the present invention is to provide the fuel with high density alcohol, described fuel quantity ga(u)ge reveals sufficiently high vapour pressure, and for example pressure can meet regulation.This is intended to strengthen cold starting performance, even for example to guarantee that in the winter time at temperature, fuel also can show good cold starting performance.
By using the C of at least one claim 1 4alcohol has solved this problem.
Basic fuel is regular price gasoline, for example white gasoline, the white gasoline that the RON providing as German and European elsewhere is 95.
Since 1984, provide as Normal (standard level) in service station, in addition provided to be used as Euro-Super (European superelevation level) from 1985, and be specified in to be used as the minimum standard of the white gasoline that SuperPlus (reinforced superelevation level) provides from 1989 in the European Standard DIN EN 228 of 1993.The composition that derives from the spark ignition fuel of German refinery with standard level, superelevation level and reinforced super Higher quality is found in for example German ScientificAssociation for Mineral Oil, Na tural Gas, in the DGMK Research Report 502-1 of and Coals (being also referred to as DGMK).In this analysis, measure the main ingredient of fuel, specifically, measure described main ingredient in the mode of mean value and scope.This analysis according to the product in winter that was 2001/2002 winter.Herein clearly with reference to this report.Specifically, 50 kinds of content with the hydrocarbon of 3 to 6 carbon atoms, 51 kinds of aromatic hydrocarbons and 3 kinds of oxygenatedchemicalss have been measured.In addition,, for all paraffin, naphthenic hydrocarbon, cycloolefin and non-ring olefin and aromatic hydrocarbons, measured the total content in every kind of situation with all representatives of same carbon content.What measure separately is the content of 10 kinds of diene and 15 kinds of polycyclic aromatic hydrocarbonss.Related spark ignition fuel is derived from 14 kinds of different raffinates.
Gained fuel package of the present invention is containing this type of basic fuel of 15 volume % to 50 volume %.
The trend (its volatility) of gasoline volatilization is the primary prerequisite as spark ignition fuel, is also basic qualitative characteristics simultaneously.Because gasoline is the mixture of many hydrocarbon, therefore it does not have the boiling point of restriction, but has the boiling range between 30 DEG C to 200 DEG C conventionally.
Fuel package of the present invention is containing the ethanol of 15 volume % to 65 volume % and the C of 15 volume % to 50 volume % 4alcohol.Certainly, amount to, comprise any other component that may exist, always obtain the summation of 100 volume %.
In principle, with respect to normal fuel, the characteristic of fuel is because the alcohol of high-content changes.A kind of this class feature is for example volatility.
Volatilely be characterised in that in most cases 30 DEG C to 200 DEG C, the boiling curve in the widest 26 DEG C to 210 DEG C temperature bands, and volatile vapour pressure that is characterised in that.Boiling curve has been described the volatilization fluid proportional under differing temps.Vapour pressure be fuel element under limiting temperature, in encloses container, be transformed into the result of vapor phase from fluid-phase.
" gasoline fraction/temperature of volatilization " function provides alleged boiling curve, and its position makes those skilled in the art can draw the conclusion relevant to fuel behavior in engine with characteristic.In principle, the volatility of spark ignition fuel must be determined in some way, makes in combustion chamber, to have the fuel-air mixture that can light in all cases.Under specific operational condition, the engine of for example cold especially or extreme heat, this prerequisite is difficult to meet, and fuel quality difference can be confirmed according to this criterion.
The ignitionability of mixture is not only subject to the impact of fuel, and is subject to the impact of engine design.Be, to there are differences aspect the driving of " richness " or " poor " mixture at engine.
With regard to winter operation, the volatility of spark ignition fuel is generally suitable for cold envrionment temperature.In order to obtain reliable cold start-up, described fuel should volatilize as much as possible.Because too low volatility will cause mixture to become poor because the insufficient and too much fuel of evaporation is condensate on intake manifold wall, therefore the low boiling curve in low temperature range and high-vapor-pressure are conducive to startup and the preheating of engine.
To thermo-motor gasoline require just the opposite.Under disadvantageous condition, the variable constituents in fuel system obtains awfully hot, makes the fuel volatilization (in oil fuel pump " formation vapor phase ") of ratio too much, and vaporizer floating chamber is left in boiling, or in injection system, forms steam cushion.Therefore, fuel is carried and is interrupted, and the excessive enrichment of mixture, and this has disadvantageous effect to transmission performance.These are upset and occur more frequently, and it is just hotter that fuel system (pump, vaporizer and fuel injection system) becomes, and fuel delivered volume and system pressure just lower.Aspect fuel, too high volatility makes himself obviously to cause disadvantageous effect.Summer environment high temperature has increased the possibility of fault.For this reason, fuel making business mixes their summer variety in some way, makes with respect to winter fuel kind, and the high and steam of boiling curve in low temperature range forces down.But this adjustment necessarily can not be excessive to cause cold start-up to produce difficulty.
According to basic fuel, especially there is the fuel mixture of high-content ethanol, conventionally can not keep the minimum vapour pressure that should keep according to draft specifies, especially winter product.Result is will have to reduce ethanol content to reach minimum vapour pressure.
Surprisingly, find, by for example, by the fuel that comprises substrate gasoline and ethanol (E85) and at least one C 4alcohol (for example can have high density C 4other fuel form of alcohol exists) mix the raising that can realize mixture vapour pressure, described vapour pressure is higher than the vapour pressure of independent fuel.In laboratory, measure the vapour pressure (according to EN 13016-1) of various ethanol and butanols mixture in super matter gasoline.
The results are shown in table 1 and 2.In every kind of situation for characterizing the by volume content of per-cent (%) meter of this combination of numeral after the character of independent combination.
Fuel of the present invention has met the requirement relating to above, and has improved specifically cold start characteristics.
Can determine in principle, for the mixture of the ethanol of basic fuel and higher proportion, if by least one C 4alcohol joins in this mixture, makes its content in gained fuel mixture equal at least 15 volume %, and the atypia that vapour pressure occurs increases.This increase of vapour pressure is that those skilled in the art are unpredictalbe.After mixing, comprise 15 volume % to 50 volume % basic fuels, 15 volume % to 65 volume % ethanol and 15 volume % to 50 volume %C 4in the fuel of alcohol, described effect is significant.After mixing, comprise 20 volume % to 46 volume % basic fuels, 20 volume % to 60 volume % ethanol and 20 volume % to 50 volume %C 4in the fuel of alcohol, and especially after mixing, comprise 19.5 volume % to 44 volume % basic fuels, 21 volume % to 59.5 volume % ethanol and 21 volume % to 49 volume %C 4in the fuel of alcohol, described effect is especially significant.Work as C 4when alcohol is the mixture of propyl carbinol (being also called as n-butyl alcohol), sec-butyl alcohol (being also called as 2-butanols) or isopropylcarbinol (being also called as 2-methyl isophthalic acid-propyl alcohol) or at least two kinds of these butanols, this effect is especially significant.
According to the analysis (distilling according to EN ISO 3405) to boiling behavior, determine the fuel that comprises ethanol and the fuel mix that comprises butanols, obtain positive effect.In mixture of the present invention, the constant rising of distillation curve of describing in approximately 20% to 90% volatilization volume range with smooth fashion, thus obtain the track similar with spark ignition fuel trace.
If C 4alcohol is isopropylcarbinol, and with regard to vapour pressure and boiling behavior, related effect is especially favourable.
With regard to being included in the ethanol in fuel described herein, inessential fuel characteristic is the generation source of ethanol substantially.But preferably, at least most of ethanol for natural origin Tathagata authigenic material will be used, because in the time of burning, this ethanol generates the carbonic acid gas of environmental protection.For the same reason, C used 4the same preferably major part of alcohol is natural origin.
In fuel of the present invention, the total content of alcohol is at least 50 volume %, but preferred at least 70 volume %.
As previously mentioned, basic fuel is the fuel as white gasoline, the white gasoline of for example current commercially available acquisition.This is mainly the compositions of mixtures of 4 to 12 hydrocarbon by carbon number.Its main ingredient is mainly paraffin, naphthenic hydrocarbon, alkene and aromatic hydrocarbons.In addition, basic fuel also can comprise oxygen-containing component.In this case, preferred ether.Press the volumeter of basic fuel, ether content preferably equals maximum 15%.As ether, very suitable is t-butyl methyl ether (being also called as MTBE) and tertiary butyl ethyl ether (being also called as ETBE) or their mixture.
The invention still further relates to and prepare the method for gained fuel as described in the present invention, using and as fuels for spark ignition engines, the especially purposes of fuels for spark ignition engines in Motor vehicles.
Gained fuel of the present invention is preferably made by the fuel mixture having existed.A kind of in these mixtures is the E85 fuel of having described, and its ratio having is that ethanol and the ratio of 70 volume % to 85 volume % is the basic fuel (mixture (I)) of 15 volume % to 30 volume %.The C of the basic fuel that other mixture comprises 30 volume % to 50 volume % and 50 volume % to 70 volume % 4alcohol (mixture (II)).The preferred blending ratio of mixture I: II is 1: 1.Mixture I can be E70 or E85 gasoline, and mixtures II can be B50 or B70 gasoline.Preferably containing the mixture (I) of 70 volume % ethanol and containing 50 volume %C 4the mixture of the mixture (II) of alcohol (especially isopropylcarbinol).The ratio of mixture (I) and mixture (II) preferably, in 40: 60 to 60: 40 scopes, is respectively 50: 50 or 1: 1 specifically.But mixture (I) can comprise the ethanol of maximum 85 volume %, and mixture (II) can comprise the C of maximum 70 volume % 4alcohol.
But substantially, C 4alcohol not only can be used as with the mixture of basic fuel and joins in the mixture of basic fuel and high-content alcohol, and C 4alcohol can also high density (maximum 100%) join in mixture below.In in the end analyzing, measure the concentration rate in gained mixture.Therefore, the invention still further relates at least one C 4alcohol improves the application of the vapour pressure of fuels for spark ignition engines, and described fuel package is containing basic fuel and ethanol.In described application, by described at least one C 4alcohol joins in the fuel that comprises basic fuel and ethanol to obtain gained fuel mixture, the C of the basic fuel that described mixture comprises 15-50 volume %, the ethanol of 15-65 volume % and 15-50 volume % 4alcohol.Volume percent (%) data in every kind of situation are all relevant to the fuel mixture of gained.
Gained fuel mixture preferably contains concentration and is less than by weight 800ppm, for example the water within the scope of 100 to 400ppm by weight.
The present invention is now only shown by way of example, referring to the data in table 1 and 2.According to EN13016-1, be determined at the vapour pressure of various ethanol and butanols mixture in the super-gasoline recording in laboratory, and be shown in table 1 and 2.
Also show the difference between expectation vapour pressure and the actual steam pressure calculating according to component relative volume amount.Calculate expectation vapour pressure according to the relative volume ratio of component.For example, the iB50 vapour pressure that the expectation vapour pressure of calculating 70 volume %iB50/30 volume %E70 mixtures is 70% adds 30% E70 vapour pressure.In table, data illustrate, use at least one C 4alcohol has improved the vapour pressure of the fuel that comprises basic fuel and ethanol, described vapour pressure exceed by by the vapour pressure of various gasoline/ethanol and gasoline/butanols mixture according to their the amount vapour pressure that adduction predicts in proportion.Therefore, for example, find that 1B50 has the vapour pressure of 56.1kPa, 2B50 has the vapour pressure of 55.7kPa, and iB50 has the vapour pressure of 55.6kPa, and iB70 has the vapour pressure of 40.7kPa, and E70 has the vapour pressure of 56.1kPa, and E85 has the vapour pressure of 40.0kPa.Measure various 50: 50 (volume/volume) mixture vapour pressures of these butanols and alcohol mixture, and find to be greater than the average vapour pressure of component mixture.Therefore, C 4alcohol has improved the vapour pressure of fuel mixture.
In table 1 and 2, also show the E70/iB50 mixture of various ratios and the expectation vapour pressure of E85/iB70 mixture and record the difference between vapour pressure, predicated value is to calculate according to the relative volume ratio of two kinds of mixtures.
Because of C 4the vapour pressure raising that alcohol causes is shown in described table.
table 1
E=ethanol
1B=1-butanols
2B=2-butanols
IB=isopropylcarbinol
50-85=alcohol content [volume percent (%)]
Gasoline=RON95 white gasoline, " super "
table 2
E=ethanol iB=isopropylcarbinol the first=the first is measured series
1B=1-butanols 50-85=alcohol content [volume percent (%)] the second=the second is measured series
2B=2-butanols gasoline=RON95 white gasoline, " super "

Claims (11)

1. at least one C 4alcohol improves the purposes of the vapour pressure of fuels for spark ignition engines, and described fuel package is containing basic fuel and ethanol, in described purposes, by described at least one C 4alcohol joins in the fuel that comprises basic fuel and ethanol to prepare gained fuel mixture, the C of the basic fuel that described fuel mixture comprises 15-50 volume %, the ethanol of 15-65 volume % and 21-50 volume % 4alcohol, wherein the vapour pressure of gained fuel mixture exceeds the vapour pressure of independent fuel.
2. according to the purposes of claim 1, wherein said gained fuel mixture comprises:
The basic fuel of 19.5 volume % to 44 volume %,
The ethanol of 21 volume % to 59.5 volume %, and
The C of 21 volume % to 49 volume % 4alcohol.
3. according to the purposes of claim 1 or 2, wherein said C 4alcohol is one or more in propyl carbinol, sec-butyl alcohol and isopropylcarbinol.
4. according to the purposes of claim 1 or 2, wherein said C 4alcohol is isopropylcarbinol.
5. according to the purposes of claim 1, the ether that wherein said basic fuel comprises 0-15 volume %.
6. according to the purposes of claim 5, wherein said ether is t-butyl methyl ether and/or tertiary butyl ethyl ether.
7. according to the purposes of claim 1 or 2, wherein the alcohol content of gained fuel mixture is at least 50 volume %.
8. according to the purposes of claim 7, wherein the alcohol content of gained fuel mixture is at least 70 volume %.
9. according to the purposes of claim 1 or 2, described purposes comprises by mixture I is mixed to prepare fuel with mixtures II, the ethanol of the basic fuel that described mixture I comprises 15-30 volume % and 70-85 volume %, the C of the basic fuel that described mixtures II comprises 30-50 volume % and 50-70 volume % 4alcohol.
10. according to the purposes of claim 9, wherein with ratio blend mixture I and the mixtures II of 1: 1 by volume.
11. according to the purposes of claim 9, and wherein mixture I is E70 or E85 gasoline, and mixtures II is B50 or B70 gasoline.
CN200980104801.XA 2008-02-12 2009-02-05 Use of alcohols in fuels for spark ignition engines Expired - Fee Related CN101981165B (en)

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DE102008008818A DE102008008818A1 (en) 2008-02-12 2008-02-12 Fuels for petrol engines
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PCT/EP2009/000787 WO2009100848A1 (en) 2008-02-12 2009-02-05 Use of alcohols in fuels for spark ignition engines

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