AU782062B2 - Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines - Google Patents

Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines Download PDF

Info

Publication number
AU782062B2
AU782062B2 AU28949/01A AU2894901A AU782062B2 AU 782062 B2 AU782062 B2 AU 782062B2 AU 28949/01 A AU28949/01 A AU 28949/01A AU 2894901 A AU2894901 A AU 2894901A AU 782062 B2 AU782062 B2 AU 782062B2
Authority
AU
Australia
Prior art keywords
volume
ethanol
dvpe
gasoline
fuel
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.)
Ceased
Application number
AU28949/01A
Other versions
AU2894901A (en
Inventor
Igor Golubkov
Angelica Hull
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.)
Individual
Original Assignee
Individual
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=20278139&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=AU782062(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Individual filed Critical Individual
Publication of AU2894901A publication Critical patent/AU2894901A/en
Assigned to HULL, ANGELICA, GOLUBKOV, IGOR reassignment HULL, ANGELICA Amend patent request/document other than specification (104) Assignors: HULL, ANGELICA
Assigned to HULL, ANGELICA reassignment HULL, ANGELICA Alteration of Name(s) of Applicant(s) under S113 Assignors: GOLUBKOV, IGOR, HULL, ANGELICA
Application granted granted Critical
Publication of AU782062B2 publication Critical patent/AU782062B2/en
Anticipated expiration legal-status Critical
Ceased 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters

Abstract

Method of reducing the vapour pressure of a C3 to C12 hydrocarbon-based motor fuel mixture containing 0.1 to 20 % by volume of ethanol for conventional spark ignition internal combustion engines, wherein, in addition to an ethanol component (b) and a C3 to C12 hydrocarbon component (a), an oxygen-containing additive (c) selected from at least one of the following types of compounds: alcohol other than ethanol, ketone, ether, ester, hydroxy ketone, ketone ester, and a heterocyclic containing oxygen, is used in the fuel mixture in an amount of at least 0.05 by volume of the total fuel, is disclosed. A mixture of fuel grade ethanol (b) and oxygen-containing additive (c) usable in the method of the invention is also disclosed. <IMAGE>

Description

WO 01/53437 PCT/SE01/00040 METHOD OF REDUCING THE VAPOUR PRESSURE OF ETHANOL-CONTAINING MOTOR FUELS FOR SPARK IGNITION COMBUSTION ENGINES This invention relates to motor fuel for spark ignition internal combustion engines.
More particularly the invention relates to a method for lowering the dry vapour pressure equivalent (DVPE) of a fuel composition including a hydrocarbon liquid and ethanol by using an oxygen-containing additive. The ethanol and DVPE adjusting components used to obtain the fuel composition are preferably derived from renewable raw materials. By means of the method of the invention motor fuels containing up to 20 by volume of ethanol meeting standard requirements for spark ignition internal combustion engines operating with gasoline are obtainable.
Background of the invention Gasoline is the major fuel for spark ignition internal combustion engines. The extensive use of gasoline results in the pollution of the environment. The combustion of gasoline derived from crude oil or mineral gas disturbs the carbon dioxide balance in the atmosphere, and causes the greenhouse effect. Crude oil reserves are decreasing steadily with some countries already facing crude oil shortages.
The growing concern for the protection of the environment, tighter requirements governing the content of harmful components in exhaust emissions, and crude oil shortages, force industry to develop urgently alternative fuels which bum more cleanly.
The existing global inventory of vehicles and machinery operating with spark ignition internal combustion engines does not allow currently the complete elimination of gasoline as a motor fuel.
WO 01/53437 PCT/SE01/00040 2 The task of creating alternative fuels for internal combustion engines has existed for a long time and a large number of attempts have been made to use renewable resources for yielding motor fuel components.
U.S. Patent No. 2,365,009, issued in 1944 describes the combination of Cl-s, alcohols and C 3 .s hydrocarbons for use as a fuel. In U.S. Patent No. 4,818,250 issued in 1989 it is proposed to use limonene obtained from citrus and other plants as a motor fuel, or as a component in blends with gasoline. In U.S. Patent No. 5,607,486 issued in 1997, there are disclosed novel engine fuel additives comprising terpenes, aliphatic hydrocarbons and lower alcohols.
Currently tert-butyl ethers are widely used as components of gasolines. Motor fuels comprising tert-butyl ethers are described in U.S. Patent No. 4,468,233 issued in 1984. The major portion of these ethers is obtained from petroleum refining, but can equally be produced from renewable resources.
Ethanol is a most promising product for use as a motor fuel component in mixtures with gasoline. Ethanol is obtained from the processing of renewable raw material, known generically as biomass, which, in turn, is derived from carbon dioxide under the influence of solar energy.
The combustion of ethanol produces significantly less harmful substances in comparison to the combustion of gasoline. However, the use of a motor fuel principally containing ethanol requires specially designed engines. At the same time spark ignition internal combustion engines normally operating on gasoline can be operated with a motor fuel comprising a mixture of gasoline and not more than about 10 by volume of ethanol. Such a mixture of gasoline and ethanol is presently sold in the United States as gasohol. Current European regulations concerning gasolines allow the addition to gasoline of up to 5 by volume of ethanol.
The major disadvantage of mixtures of ethanol and gasoline is that for mixtures containing up to about 20 by volume of ethanol there is an increase in the dry vapour pressure equivalent as compared to that of the original gasoline.
WO 01/53437 PCT/SE01/00040 3 Figure 1 shows the behaviour of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content of mixtures of ethanol and gasoline A92 summer, and gasoline A95 summer and winter at 37.8 0 C.The gasolines known as A92 and are standard gasolines purchased at gas stations in the United States and Sweden. Gasoline A92 originated in the United States and gasoline A95, in Sweden.
The ethanol employed was fuel grade ethanol produced by Williams, USA. The DVPE of the mixtures was determined according to the standard ASTM D5191 method at the SGS laboratory in Stockholm, Sweden.
For the range of concentrations by volume of ethanol between 5 and 10% which is of particular interest for use as a motor fuel for standard spark ignition engines, the data in Fig. 1 show that the DVPE of mixtures of gasoline and ethanol can exceed the DVPE of source gasoline by more than 10%. Since the commercial petroleum companies normally supply the market with gasoline already at the maximum allowed DVPE, which is strictly limited by current regulations, the addition of ethanol to such presently commercially available gasolines is not possible.
It is known that the DVPE of mixtures of gasoline and ethanol can be adjusted. U.S.
Patent No. 5,015,356 granted on May 14, 1991 proposes reformulating gasoline by removing both the volatile and non-volatile components from C4 C12 gasoline to yield either C6 Cg or C6 C1o intermediate gasoline. Such fuels are said to better facilitate the addition of alcohol over current gasoline because of their lower dry vapour pressure equivalent (DVPE). A disadvantage of this method of adjusting the DVPE of mixtures of gasoline and ethanol is that in order to obtain such a mixture it is necessary to produce a special reformulated gasoline, which adversely affects the supply chain and results in increased prices for the motor fuel. Also, such gasolines and their mixtures with ethanol have a higher flash point, which impairs their performance properties.
It is known that some chemical components decrease DVPE when added to gasoline or to a mixture thereof with ethanol. For example, U.S. Patent No. 5,433,756 granted on July 18, 1995 discloses chemical clean-combustion-promoter compounds comprising, in addition to gasoline, ketones, nitro-paraffin and also alcohols other than ethanol. It is noted that the composition of the catalytic cleancombustion-promoter disclosed in the patent reduces the DVPE of gasoline fuel.
WO 01/53437 PCT/SE01/00040 4 Nothing is mentioned in this patent about the impact of the clean-combustionpromoter composition on the DVPE of mixtures of gasoline and ethanol.
U.S. Patent No. 5,688,295 granted on November 18, 1997 provides a chemical compound as an additive to gasoline or as a fuel for standard gasoline engines. In accordance with the invention, an alcohol-based fuel additive is proposed. The fuel additive comprises from 20 70% alcohol, from 2.5 20% ketone and ether, from 0.03 20% aliphatic and silicon compounds, from 5 20% toluene and from 4 mineral spirits. The alcohol is methanol or ethanol. It is noted in the patent that the additive improves gasoline quality and specifically decreases DVPE. The disadvantages of this method of motor fuel DVPE adjustment are that there is a need for large quantities of the additive, namely, not less than 15 by volume of the mixture; and the use of silicon compounds, which form silicon oxide upon combustion, results in increased engine wear.
In W09743356 a method for lowering the vapour pressure of a hydrocarbon-alcohol blend by adding a co-solvent for the hydrocarbon and alcohol to the blend, is described. A spark ignition motor fuel composition is also disclosed, including a hydrocarbon component of Cs Ca straight-chained or branched alkanes, essentially free of olefins, aromatics, benzene and sulphur, in which the hydrocarbon component has a minimum anti-knock index of 65, according to ASTM D2699 and D2700 and a maximum DVPE of 15 psi, according to ASTM D5191; a fuel grade alcohol; and a co-solvent for the hydrocarbon component and alcohol in which the components of the fuel composition are present in amounts selected to provide a motor fuel with a minimum anti-knock index of 87 and a maximum DVPE of 15 psi. The co-solvent used is biomass-derived 2-methyltetrahydrofuran (MTHF) and other heterocyclical ethers such as pyrans and oxepans, MTHF being preferred.
The disadvantages of this method for adjusting the dry vapour pressure equivalent of mixtures of hydrocarbon liquid and ethanol are the following: It is necessary to use only hydrocarbon components Cs Ca which are straightchained or branched alkanes free of such unsaturated compounds as olefins, benzene and other aromatics, (ii) free of sulphur and, as follows from the description of the invention, (iii) the hydrocarbon component is a coal gas condensate or natural gas condensate; It is necessary to use as a co-solvent for the hydrocarbon component and ethanol only one particular class of chemical compounds containing oxygen; namely, ethers, including short-chained and heterocyclic ethers; It is necessary to use a large quantity of ethanol in the fuel, not less than It is necessary to use a large quantity of co-solvent, not less than 20%, of 2-methyltetrahydrofuran; and It is required to modify the spark ignition internal combustion engine when operating with such fuel composition and, specifically, one must change the software of the on-board computer or replace the on-board computer itself.
Accordingly, it is an object of the present invention to provide a method by which "the above-mentioned drawbacks of the prior art can be overcome. It is a primary object of the invention to provide a method of reducing the vapour pressure of a C 3 to C 1 2 hydrocarbon based fuel mixture containing up to 20% by volume of ethanol for conventional gasoline engines to not more than the vapour pressure of the C 3 to C 1 2 o* *hydrocarbon itself, or at least so as to meet the standard requirement on gasoline fuel.
Summary of the Invention S 20 According to a first embodiment the present invention provides a method of reducing the vapour pressure of a C 3
-C
1 2 hydrocarbon-based motor fuel mixture for conventional spark ignition internal combustion engines containing 0.1 to 20% by volume of ethanol, not more than 0.25% by weight of water according to ASTM D 6304, and not more than 7% by weight of oxygen according to ASTM D 4815, wherein, in addition to a
C
3
-C
1 2 hydrocarbon component and an ethanol component an oxygen-containing component is present in the fuel mixture in an amount from 0.05 to 15% by volume of the total volume of the fuel mixture; the component being selected from at least one of the following types of compounds: alkanol, having from 3 to 10 carbon atoms; dialkyl ether, having from 6 to 10 carbon atoms; ketone, having from 4 to 9 carbon atoms; alkyl ester of alkanoic acid, having from 5 to 8 carbon atoms; hydroxyketone, having from 4 to 6 carbon atoms; ketone ester of alkanoic acid, having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: [R:\LIBH]4802.doc:MQT tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl-4-oxytetrahydropyran, and the mixtures thereof; and a component selected from at least one C 6
-C
2 hydrocarbon, is present in the s fuel mixture in an amount such that the ratio is from 1:200 to 200:1 by volume.
According to a second embodiment the present invention provides a C 3
-C
1 2 hydrocarbon-based motor fuel composition for a conventional internal combustion spark ignition engine, containing from 0.1 to 20% by volume of ethanol, not more than 0.25% 0o by weight of water according to ASTM D6304, and not more than 7% by weight of oxygen according to ASTM D4815, having a reduced vapour pressure, comprising: a C 3
-C
1 2 hydrocarbon component; (b)a fuel grade ethanol in an amount of 0.1-20% by volume of the total volume of the motor fuel composition; s15 an oxygen-containing component comprising at least one of the following types of compounds: alkanol having from 3 to 10 carbon atoms; dialkyl ether having from 6 to 10 carbon atoms; ketone having from 4 to 9 carbon atoms; S 20 alkyl ester ofalkanoic acid having from 5 to 8 carbon atoms; hydroxyketone having from 4 to 6 carbon atoms; S- ketone ester ofalkanoic acid having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl-4-oxytetrahydropyran, aod mixtures thereof, said oxygen-containing component being present in an amount of 0.05 to 15% by volume of the total volume of the motor fuel composition; at least one C 6
-C
12 hydrocarbon, preferably C 8
-C
11 hydrocarbon, present in an amount such that the ratio is from 1:200 to 200:1 by volume.
According to a third embodiment the present invention provides a mixture of a fuel grade ethanol an oxygen-containing component and at least one C6-C12 hydrocarbon which can be used in the method of the first embodiment, wherein: the ethanol component is present in an amount of 0.5 to 99.5%, by volume of the total volume of the mixture; [R:\LIBH]4802.doc:MQT the oxygen-containing component is selected from at least one of the following types of compounds: alkanol having from 3 to 10 carbon atoms; dialkyl ether having from 6 to 10 carbon atoms; ketone having from 4 to 9 carbon atoms; alkyl ester ofalkanoic acid having from 5 to 8 carbon atoms; hydroxyketone having from 4 to 6 carbon atoms; ketone ester of alkanoic acid having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl- 4-oxytetrahydropyran, and mixtures thereof, and is present in an amount of 0.5 to 99.5%, by volume of the total volume of the mixture; component comprising at least one C 6
-C
1 2 hydrocarbon, preferably C 8 15 CII hydrocarbon, in an amount present in an amount such that the ratio is from 1:200 to 200:1 by volume.
S. According to a fourth embodiment the present invention provides use of the o Smixture of the third embodiment as a motor fuel in a modified internal combustion spark ignition engine.
20 According to a fifth embodiment the present invention provides use of the mixture of the third embodiment for obtaining a gasoline fuel, containing components o for conventional internal combustion spark ignition engines and *oo adjusting the octane number of such a fuel to a desired level by mixing a corresponding amount of said mixture with a conventional gasoline fuel while maintaining or decreasing the vapour pressure of the thus-obtained fuel composition as compared to the level of the vapour pressure of the gasoline component alone.
According to a sixth embodiment the present invention provides use of the composition of the second embodiment for reducing the fuel consumption as compared to corresponding gasoline-ethanol mixture comprising components According to a seventh embodiment the present invention provides use of the composition of the second embodiment for reducing the content of harmful substances in the exhaust emissions as compared to corresponding gasoline-ethanol mixture comprising components The above-mentioned object of the present invention has been accomplished by means of the method of the preamble of claim 1, characterised in that an oxygen- [R:\LIBH]4802.doc:MQT containing additive selected from at least one of the following types of compounds: alcohol other than ethanol, ketone, ether, ester, hydroxy-ketone, ketone ester, and a heterocyclic compound containing oxygen, is used in the fuel mixture in an amount of at least 0.05% by volume of the overall fuel mixture.
[R:\LIBH]4802.doc:MQT WO 01/53437 PCT/SE01/00040 6 The present inventors have found that specific types of compounds exhibiting an oxygen-containing group surprisingly lower the vapour pressure of a gasolineethanol mixture.
This effect can unexpectedly be further enhanced by means of specific C 6
C
1 2 hydrocarbon compounds.
They have also found that the octane number of the resulting hydrocarbon based fuel mixture surprisingly can be maintained or even increased by using the oxygencomponent of the present invention.
According to the present method up to about 20 by volume of fuel grade ethanol can be used in the whole fuel compositions. The oxygen-containing additives (c) used can be obtained from renewable raw materials, and the hydrocarbon component used can for example be any standard gasoline (which does not have to be reformulated) and can optionally contain aromatic fractions and sulphur, and also hydrocarbons obtained from renewable raw materials.
By means of the method of the invention fuels for standard spark ignition internal combustion engines can be prepared, which fuels allow such engines to have the same maximum performance as when operated on standard gasoline currently on the market. A decrease in the level of toxic emissions in the exhaust and a decrease in the fuel consumption can also be obtained by using the method of the invention.
According to one aspect of the invention, in addition to the dry vapour pressure equivalent (DVPE), the anti-knock index (octane number) can also be desirably controlled.
It is yet another object to provide an additive mixture of fuel grade ethanol and oxygen-containing additive and optionally, the further component being individual hydrocarbons of the C 6
-C
1 2 fraction or their mixtures, which additive mixture subsequently can be used in the inventive method, added to the hydrocarbon component The mixture of and and optionally can also be used per se as a fuel for modified engines, not standard-type gasoline engines. The WO 01/53437 PCT/SE01/00040 7 additive mixture can also be used for adjusting the octane number and/or for lowering the vapour pressure of a high vapour pressure hydrocarbon component.
Further objects and advantages of the present invention will be evident from the following detailed description, examples and dependent claims.
Brief description of the drawings In Figure 1, the behaviour of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content of prior art mixtures of ethanol and gasoline is shown.
In Figure 2, the behaviour of the dry vapour pressure equivalent (DVPE) of different fuels of the present invention as a function of the ethanol content thereof is shown.
DETAILED DESCRIPTION OF THE PRESENT INVENTION The present method enables the use of C 3
C
12 hydrocarbon fractions as hydrocarbon component including narrower ranges within this broader range, without restriction on the presence of saturated and unsaturated hydrocarbons, aromatics and sulphur. In particular, the hydrocarbon component can be a standard gasoline currently on the market, as well as other mixtures of hydrocarbons obtained in the refining of petroleum, off-gas of chemical-recovery coal carbonisation, natural gas and synthesis gas. Hydrocarbons obtained from renewable raw materials can also be included. The C3 C012 fractions are usually prepared by fractional distillation or by blending various hydrocarbons.
Importantly, and as previously mentioned, the component can contain aromatics and sulphur, which are either co-produced or naturally found in the hydrocarbon component.
According to the method of the present invention the DVPE can be reduced for fuel mixtures containing up to 20% volume of ethanol, calculated as pure ethanol. According to a preferred embodiment the vapour pressure of the hydrocarbon based ethanol-containing fuel mixture is reduced by 50% of the ethanol-induced vapour pressure increase, more preferably by 80%, and even more preferably the vapour WO 01/53437 PCT/SE01/00040 8 pressure of the hydrocarbon based ethanol-containing fuel mixture is reduced to a vapour pressure corresponding to that of the hydrocarbon component alone, and/or to the vapour pressure according to any standard requirement on commercially sold gasoline.
As will be evident from the examples, the DVPE can be reduced if desired to a level even lower than that of the hydrocarbon component used.
According to a most preferred embodiment the other properties of the fuel, such as for example the octane number, are kept within the required standard limits.
This is accomplished by adding to the motor fuel composition at least one oxygencontaining organic compound other than ethanol. The oxygen-containing organic compound enables adjustment of the dry vapour pressure equivalent, (ii) the anti-knock index and other performance parameters of the motor fuel composition as well as (iii) the reduction of the fuel consumption and the reduction of toxic substances in the engine exhaust emissions. The oxygen-containing compound has oxygen bound in at least any one of the following functional groups: O O I II I I II I -C-O-H -C-O-C- 0 H H O H II I I II I II I I I I I
-C-C-C-O-C-
H 0-H H H C, C-C I -C C- C C-O-H I I -c Ic. c- O H Such functional groups are present, for example, in the following classes of organic compounds and which can be used in the present invention: alcohols, ketones, ethers, esters, hydroxy-ketones, ketone esters, and heterocyclics with oxygencontaining rings.
WO 01/53437 PCTISE01/00040 9 The fuel additive can be derived from fossil-based sources or preferably from renewable sources such as biomass.
The oxygen-containing fuel additive can typically be an alcohol, other than ethanol. In general, aliphatic or alicyclic alcohols, both saturated and unsaturated, preferably alkanols, are employed. More preferably, alkanols of the general formula: R-OH where R is alkyl with 3 to 10 carbon atoms, most preferably 3 to 8 carbon atoms, such as propanol, isopropanol, n-butanol, isobutanol, tert-butanol, npentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, diethylcarbinol, diisopropylcarbinol, 2-ethylhexanol, 2,4,4-trimethylpentanol, 2,6-dimethyl-4-heptanol, linalool, 3,6-dimethyl-3-octanol, phenol, phenylmethanol, methylphenol, methylcyclohexanol or similar alcohols, are employed, as well as their mixtures.
The component can also be an aliphatic or alicyclic ketone, both saturated and 0
II
unsaturated, of the general formula R C R' where R and R' are the same or different and are each C1-C hydrocarbons, which also can be cyclic, and are preferably CI-C4 hydrocarbons. Preferred ketones have a total of 4 to 9 carbon atoms and include methylethyl ketone, methylpropyl ketone, diethylketone, methylisobutyl ketone, 3-heptanone, 2-octanone, diisobutyl ketone, cyclohexanon, acetofenone, trimethylcycohexanone, or similar ketones, and mixtures thereof.
The component can also be an aliphatic or alicyclic ether, including both saturated and unsaturated ethers, of the general formula wherein R and R' are the same or different and are each a Ci-Clo hydrocarbon group. In general, lower (Ci-C6) dialkyl ethers are preferred. The total number of carbon atoms in the ether is preferably from 6 to 10. Typical ethers include methyltertamyl ether, methylisoamyl ether, ethylisobutyl ether, ethyltertbutyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, anisole, methylanisole, phenetole or similar ethers and mixtures thereof.
WO 01/53437 PCT/SE01/00040 The component may further be an aliphatic or alicyclic ester, including saturated 0
II
and unsaturated esters, of the general formula R C- 0 R' where R and R' are the same or different. R and R' are preferably hydrocarbon groups, more preferably alkyl groups and most preferably alkyl and phenyl having 1 to 6 carbon atoms. Especially preferred is an ester where R is C -C 4 and R' is C4-C6. Typical esters are alkyl esters of alkanoic acids, including n-butylacetate, isobutylacetate, tertbutylacetate, isobutylpropionate, isobutylisobutyrate, n-amylacetate, isoamylacetate, isoamylpropionate, methylbenzoate, phenylacetate, cyclohexylacetate, or similar esters and mixtures thereof. In general, it is preferred to employ an ester having from 5 to 8 carbon atoms.
The additive can simultaneously contain two oxygen-containing groups connected in the same molecule with different carbon atoms.
The additive can be a hydroxyketone. A preferred hydroxyketone has the general formula: Ri H R I I I R-C-C-C-R or R-C-C-Ri I I II II I H-O H O 0 0-H where R is hydrocarbyl, and R 1 is hydrogen or hydrocarbyl, preferably lower alkyl, i.e. (C 1
-C
4 In general, it is preferred to employ a ketol having 4 to 6 carbon atoms.
Typical hydroxy-ketones include 1-hydroxy-2-butanone, 3-hydroxy-2-butanone, 4hydroxy-4-methyl-2-pentanone, or similar ketols or mixture thereof.
In yet another embodiment the fuel additive is a ketone ester, preferably of the general formula:
H
I
R-C-C-C-O-R
I I II 0 H O where R is hydrocarbyl, preferably lower alkyl, i.e. (Ci-C4).
WO 01/53437 PCT/SE01/00040 11 Typical ketone esters include methylacetoacetate, ethyl acetoacetate and tert-butyl acetoacetate. Preferably, such ketone esters have 6 to 8 carbon atoms.
The additive can also be a ring-oxygen-containing heterocyclic compound and, preferably, the oxygen-containing heterocycle has a C 4 Cs ring. More preferably, the heterocycle additive has a total of 5 to 8 carbon atoms. The additive can preferably have the formula or as follows: R Ri R R R R R C 'C-C R-C C-R O 0 R O R R R 1 2 where R is hydrogen or hydrocarbyl, preferably -CH 3 and RI is -CH 3 or -OH, or -CH20H, or CHaCO 2
CH
2 A typical heterocyclic additive is tetrahydrofurfuryl alcohol, tetrahydrofurfurylacetate, dimethyltetrahydrofurane, tetramethyltetrahydrofurane, methyltetrahydropyrane, 4-methyl-4-oxytetrahydropyrane or similar heterocyclic additives, or mixtures thereof.
Component can also be a mixture of any of the compounds set out above from one or more of the above-mentioned different compound classes.
Suitable fuel grade ethanol to be used according to the present invention can readily be identified by the person skilled in the art. A suitable example of the ethanol component is ethanol containing 99.5% of the main substance. Any impurities included in the ethanol in an amount of at least 0.5 by volume thereof and falling within the above-mentioned definition of component should be taken into account when determining the amount used of component That is, such impurities must be included in an amount of at least 0.5% in the ethanol in order to be taken into account as a part of component Any water, if present in the ethanol, should preferably amount to no more than about 0.25 by volume of the total fuel mixture, in order to meet the current standard requirements on fuels for gasoline engines.
WO 01/53437 PCT/SE01/00040 12 Thus, a denatured ethanol mixture as supplied to the market, containing about 92% of ethanol, hydrocarbons and by-products, can also be used as the ethanol component in the fuel composition according to the invention.
Unless otherwise indicated all amounts are in by volume based on the total volume of the motor fuel composition.
Generally, the ethanol is employed in amounts from 0. 1% to 20%, typically from about 1% to 20 by volume, preferably 3% to 15 by volume and more preferably from about 5 to 10 by volume. The oxygen-containing additive is generally employed in amounts from 0.05% to about 15 by volume, more generally from 0.1 to about 15 by volume, preferably from about 3 10 by volume and most preferably from about 5 to 10 by volume.
In general, the total volume of ethanol and oxygen-containing additive employed is from 0. 15 to 25 by volume, normally from about 0.5 to 25 by volume, preferably from about 1 to 20 by volume, more preferably from 3 to 15 by volume, and most preferably from 5 to 15 by volume.
The ratio of ethanol to oxygen-containing additive in the motor fuel composition is thus generally from 1:150 to 400:1, and is more preferably from 1:10 to 10:1.
The total oxygen content of motor fuel composition based on the ethanol and the oxygen additive, expressed in terms of weight oxygen based on total weight of motor fuel composition, is preferably no greater than about 7 more preferably no greater than about 5 wt.%.
According to a preferred embodiment of the invention to obtain a motor fuel suitable for the operation of a standard spark ignition internal combustion engine the aforesaid hydrocarbon component, ethanol, and additional oxygen-containing component are admixed to obtain the following properties of the resulting motor fuel composition: density at 15°C and at normal atmospheric pressure of not less than 690 kg/m 3 WO 01/53437 PCT/SE01/00040 13 oxygen content, based on the amount of oxygen-containing components, of not more than 7% w/w of the motor fuel composition; anti-knock index (octane number) of not lower than the anti-knock index (octane number) of the source hydrocarbon component and preferably for 0.5(RON+MON) of not less than dry vapour pressure equivalent (DVPE) essentially the same as the DVPE of the source hydrocarbon component and preferably from 20 kPa to 120 kPa; acid content of not more than 0.1% by weight HAc; pH from 5 to 9; aromatic hydrocarbons content of not more than 40 by volume, including benzene, and for benzene alone, not more than 1 by volume; limits of evaporation of the liquid at normal atmospheric pressure in of source volume of the motor fuel composition: initial boiling point, min volume (at 70°C, min) of the liquid 25% by evaporated volume; volume (at 100°C, min) of the liquid 50% by evaporated volume; volume (at 150°C, min) of the liquid 75% by evaporated volume; volume (at 190*C, min) of the liquid 95% by evaporated volume; residue of distillation, max. 2% by volume; final boiling point, max. 2050C; sulfur content of not more than WO 01/53437 PCT/SE01/00040 14 resins content of not more than 2mg/ 100ml.
According to a preferred embodiment of the method of the invention the hydrocarbon component and ethanol should be added together, followed by the addition of the additional oxygen-containing compound or compounds to the mix. Afterwards, the resulting motor fuel composition should preferably be maintained at a temperature not lower than -35°C, for at least about one hour. It is a feature of this invention that the components of the motor fuel composition can be merely added to each other to form the desired composition. It is generally not required to agitate or otherwise provide any significant mixing to form the composition.
According to a preferred embodiment of the invention to obtain a motor fuel composition suitable for operating a standard spark ignition internal combustion engine and with a minimal harmful impact on the environment, it is preferable to use oxygen-containing component(s) originating from renewable raw material(s).
Optionally, a component can be used for further lowering the vapour pressure of the fuel mixture of components and An individual hydrocarbon selected from a C 6
C
12 fraction of aliphatic or alicyclic saturated and unsaturated hydrocarbons can be used as component Preferably the hydrocarbon component is selected from a Cs-Cnl fraction. Suitable examples of are benzene, toluene, xylene, ethylbenzene, isopropylbenzene, isopropyltoluene, diethylbenzene, isopropylxylene, tert-butylbenzene, tert-butyltoluene, tert-butylxylene, cyclooctadiene, cyclooctotetraene, limonene, isooctane, isononane, isodecane, isooctene, myrcene, allocymene, tert-butylcyclohexane or similar hydrocarbons and mixtures hereof.
Hydrocarbon component can also be a fraction boiling at 100-200°C, obtained in the distillation of oil, bituminous coal resin, or synthesis gas processing products.
As already mentioned the invention further relates to an additive mixture consisting of components and and, optionally also component which subsequently can be added to the hydrocarbon component and is also possible to use as such as a fuel for a modified spark ignition combustion engine.
WO 01/53437 PCT/SE01/00040 The additive mixture preferably has a ratio of ethanol to additive of 1:150 to 200:1 by volume. According to a preferred embodiment of the additive mixture, said mixture comprises the oxygen-containing component in an amount from 0.5 up to 99.5 by volume, and ethanol in an amount from 0.5 up to 99.5 by volume, and component comprising at least one C6 C12 hydrocarbon, more preferably C 8 -CLI hydrocarbon, in an amount from 0 up to 99 by volume, preferably from 0% up to 90%, more preferably from 0 up to 79,5%, and most preferably from 5 up to 77% of the additive mixture. The additive mixture preferably has a ratio of ethanol to the sum of the other additive components from 1:200 to 200:1 by volume, more preferable a ratio of ethanol to the sum of the components (d) is from 1:10 to 10:1 by volume.
The octane number of the additive mixture can be established, and the mixture be used to adjust the octane number of the component to a desired level by admixing a corresponding portion of the mixture to component As examples demonstrating the efficiency of the present invention the following motor fuel compositions are presented which are not to be construed as limiting the scope of the invention, but as merely providing illustrations of some of the presently preferred embodiments of this invention.
As will be obvious to the person skilled in the art, all the fuel compositions of the following Examples can of course also be obtained by first preparing an additive mixture of components and and optionally which mixture thereafter can be added to the component or vice versa. In this case a certain amount of mixing may be required.
EXAMPLES
To prepare the blended motor fuel the following was used as the components and fuel grade ethanol purchased in Sweden at Sekab and in the USA from ADM Corp. and Williams; WO 01/53437 PCT/SE01/00040 -oxygen-containing compounds, individual unsubstituted hydrocarbons and mixtures hereof purchased in Germany from Merck and in Russia from Lukoil.
Naphtha, which is an oil straight run gasoline containing aliphatic and alicyclic saturated and unsaturated hydrocarbons. Alkylate, which is a hydrocarbon fraction consisting almost completely of isoparaffine hydrocarbons obtained in alkylation of isobutene by butanol. Alkylbenzene, which is a mixture of aromatic hydrocarbons obtained in benzene alkylation. Mostly, technical grade alkylbenzene comprises ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene and others.
All the testing of source gasolines and ethanol-containing motor fuels, including those comprising the components of this invention was performed employing the standard ASTM methods at the laboratory of SGS in Sweden and at Auto Research Laboratories, Inc., USA.
The drivability testing was performed on a 1987 VOLVO 240 DL according to the standard test method EU2000 NEDC EC 98/69.
The European 2000 (EU 2000) New European Driving Cycle (NEDC) standard test descriptions are identical to the standard EU/ECE Test Description and Driving Cycle (91/441 EEC resp. ECE-R 83/01 and 93/116 EEC). These standardised EU tests include city driving cycles and extra urban driving cycles and require that specific emission regulations be met. Exhaust emission analysis is conducted with a constant volume sampling procedure and utilises a flame ionisation detector for hydrocarbon determination. Exhaust Emission Directive 91/441 EEC (Phase I) provides specific CO, (HC NO) and (PM) standards, while EU Fuel Consumption Directive 93/116 EEC (1996) implements consumption standards.
The testing was performed on a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No. LG4F20-87) developing 83 kW at 90 revolutions/second and a torque of 185 Nm at 46 revolutions/second.
EXAMPLE 1 WO 01/53437 PCT/SE01100040 17 Example 1 demonstrates the possibility of reducing the dry vapour pressure equivalent of the ethanol-containing motor fuel for the cases when gasolines with dry vapour pressure equivalent according to ASTM D-5191 at a level of 90 kPa (about 13 psi) are used as a hydrocarbon base.
To prepare the mixtures of this composition winter gasolines A92, A95, and A98, presently sold on the market and purchased in Sweden from Shell, Statoil, and Preem, were used.
Fig. 1 demonstrates the behaviour of the DVPE of the ethanol-containing motor fuel based on winter A95 gasoline. The ethanol-containing motor fuels based on winter A92 and A98 used in this example also demonstrate a similar behaviour.
The source gasoline comprised aliphatic and alicyclic C4-C12 hydrocarbons, including both saturated and unsaturated ones.
The winter A92 gasoline used had the following specification: DVPE 89,0 kPa Anti-knock index 0.5(RON MON)=87.7 The fuel 1-1 (not according to the invention) contained A92 winter gasoline and ethanol and had the following properties for different ethanol contents: A92 Ethanol 95 5 by volume DVPE 94.4 kPa MON) 89.1 A92 Ethanol 90 10 by volume DVPE 94.0 kPa 0 .5(RON MON) 90.2 The following different embodiments of the fuels 1-2 and 1-3 demonstrate the possibility of adjusting the dry vapor pressure equivalent (DVPE) of the ethanolcontaining motor fuel based on winter A92 gasoline.
WO 01/53437 PCTISE01/00040 18 The inventive fuel 1-2 contained A92 winter gasoline ethanol and oxygencontaining additives and had the following properties for the various compositions: A92 Ethanol Isobutyl acetate 88.5 4.5 7 by volume DVPE 89.0 kPa MON) 89.9 A92 Ethanol Isoamyl acetate 88 5 7 by volume DVPE 88.6 kPa MON) 89.0 A92 Ethanol Diacetone alcohol 88.5 4.5 7 by volume DVPE 89.0 kPa 0.5(RON MON) 89.65 A92 Ethanol: Ethylacetoacetate 90.5 2.5 7 by volume DVPE 89.0 kPa MON) 87.8 A92 Ethanol: Isoamylpropionate 87.5 5.5 7 by volume DVPE 88.7 kPa MON) 90.4 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel induced by the presence of ethanol to the level of the DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
A92 Ethanol 3-Heptanone 85 7.5 7.5 by volume DVPE 90.0 kPa MON) 89.9 A92 Ethanol: 2,6-dimethyl-4-heptanol 85 8.5 6.5 by volume WO 01/53437 PCTSE01/00040 19 DVPE 90.0 kPa MON) 90.3 A92 Ethanol Diisobutyl ketone 85 7.5 7.5 by volume DVPE 90.0 kPa MON) 90.25 The inventive fuel 1-3 contained A92 winter gasoline ethanol oxygencontaining additives and hydrocarbons C 6
-C
1 2 and had the following properties for the various compositions: A92 Ethanol Isoamyl alcohol Alkylate 79 9 2 10 by volume The boiling temperature of the alkylate is 100-130°C DVPE 88.5 kPa 0.5(RON MON) 90.25 A92 Ethanol: Isobutyl acetate Naphtha 80 5 5 10 by volume The boiling temperature for the naphtha is 100-200°C DVPE 88.7 kPa 0.5(RON MON) 88.6 A92 Ethanol Tert-butanol: Naphtha 81 5 5 9 by volume The boiling temperature for the naphtha is 100-200°C DVPE 87.5 kPa 0.5(RON MON) 89.6 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel induced by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
A92 Ethanol Isoamyl alcohol Benzene Ethylbenzene Diethyl benzene 82.5 9.5 0.5 0.5 3 4 by volume WO 01/53437 PCT/SE01/00040 DVPE 90 kPa MON) 91.0 A92 Ethanol: Isobutyl acetate Toluene 82.5 9.5 0.5 7.5 by volume DVPE 90 kPa MON) 90.8 A92 Ethanol Isobutanol Isoamyl alcohol m-Xylene 82.5 9.2 0.2 0.6 7.5 by volume DVPE 90 kPa MON) 90.9 The following compositions 1-5 to 1-6 demonstrate the possibility of adjusting the dry vapor pressure equivalent (DVPE) of the ethanol-containing motor fuel based on winter A98 gasoline.
The winter A98 gasoline had the following specification: DVPE 89,5 kPa Anti-knock index 0.5(RON MON)=92.35 The comparative fuel 1-4 contained A98 winter gasoline and ethanol and had the following properties for the various compositions: A98 Ethanol 95 5 by volume DVPE 95.0 kPa MON) 92.85 A98 Ethanol 90 10 by volume DVPE 94.5 kPa 0.5(RON MON) 93.1 The fuel 1-5 contained A98 winter gasoline ethanol and oxygen-containing additives and had the following properties for the various compositions: A98 Ethanol Isobutanol 84 :9 7 by volume WO 01/53437 WO 0153437PCT/SEOI/00040 21 DVPE =88.5 kPa, MON) 93.0 A98 Ethanol :Tert-butylacetate 84 :9 7 by volume DVPE =89.5 kPa MON) 93.3 A98: Ethanol: Benzyl alcohol 85: 7.5: 7.5 by volume DVPE =89.5 kPa 0.5(RON MON) =93.05 A98 Ethanol: Cyclohexanone 85: 7.5: 7.5. by volume DVPE =88.0 kPa MON) =92.9 A98 Ethanol Diethyl ketone 85 7.5: 7.5 by volume DVPE 89.0 kPa MON) 92.85 A98 Ethanol Methyipropyl ketone 85 7.5 7.5 by volume DVPE =89.5 kPa MON) 93.0 A98 Ethanol Methylisobutyl ketone =8 5 :7.5 7.5 by volume DVPE =89.0OkPa MON) 92.65.
A98 Ethanol: 3-heptanone =85 7.5 7.5 by volume DVPE =89.5 kPa.
0.5(RON MON) 92.0 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in WO 01/53437 WO 0153437PCT/SE01/00040 22 compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
A98: Ethanol: Methylisobutyl ketone =85: 8 7 by volume DVPE =90.0OkPa MON) 92.7 A98 Ethanol: Cyclohexanone 85: 8.5 6.5 by volume DVPE 90.0 kPa 0.5(RON MON) 93.0 A98: Ethanol: Methylphenol. 85: 8 7 by volume DVPE 90.0 kPa MON) 93.05 The fuel 1-6 contained A98 winter gasoline ethanol oxygen-containing additives and C 6
-C
12 hydrocarbons and had the following properties for the various compositions: A98 Ethanol :Isoamyl. alcohol Isooctane =80 5 5 :10 by volume DVPE 82.0 kPa MON) 93.2 A98: Ethanol Isoamyl alcohol :m-Isopropyl toluene =78.2 6.1 6.1 :9.6 by volume DVPE 8 1.0 kPa MON) 93.8 A98 Ethanol: Isobutanol Naphtha 80: 5: 5: 10 by volume The boiling point of the naphitha is 100-200*C.
DVPE 82.5 kPa MON) 92.35 WO 01/53437 PCT/SE01/00040 23 A98 Ethanol: Isobutanol: Naphtha: m-Isopropyl toluene 80 5 5 5 by volume The boiling point of the naphtha is 100-200 0
C.
DVPE 82.0 kPa 0.5(RON MON) 93.25 A98 Ethanol Tert-butyl acetate Naphtha 83 5 5 7 by volume The boiling temperature of the naphtha is 100-200 0
C
DVPE 82.1 kPa 0.5(RON MON) 92.5 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
A98 Ethanol Isoamyl alcohol: Isooctane 85 5 5 5 by volume DVPE 90.0 kPa 0.5(RON MON) 93.3 A98 Ethanol Isobutanol Naphtha 85 5 5 5 by volume The boiling temperature of the naphtha is 100-200°C DVPE 90.0 kPa 0.5(RON MON) 93.0 A98 Ethanol Isobutanol Isopropyl xylene 85 9.5 0.5 5 by volume DVPE 90 kPa MON) 93.1 The motor fuel compositions below demonstrate that it might be necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol below the level of DVPE of the source gasoline. Normally, this is required when DVPE of the source gasoline is higher than the limits of the regulations in force for the corresponding WO 01/53437 PCT/SE01/00040 24 gasoline. In this way, for example, it is possible to transform the winter grade gasoline into the summer grade gasoline. The DVPE level for the summer gasoline is kPa.
A98 Ethanol Isobutanol Isooctane Naphtha 60 9.5 0.5 15 15 by volume The boiling point of the naphtha is 100-200 0
C.
DVPE 70 kPa MON) 92.85 A98 Ethanol: Isobutanol Allcylate Naphtha 60 9.5 0.5 15 15 by volume The boiling point of the naphtha is 100-200 0
C.
The boiling point of the alkylate is 100-130oC.
DVPE 70 kPa MON) 92.6 A98 Ethanol Tert-butyl acetate Naphtha 60 9 3 28 by volume The boiling point of the naphtha is 100-200°C.
DVPE 70 kPa MON) 91.4 The following fuels 1-8, 1-9 and 1-10 demonstrate the possibility of adjusting the dry vapor pressure equivalent (DVPE) of the ethanol-containing motor fuel based on winter A95 gasoline.
The winter A95 gasoline had the following specification: DVPE 89.5 kPa Anti-knock index 0.5(RON MON)= 90.1 Testing in accordance with the standard test method EU 2000 NEDC EC 98/69 as described above demonstrated the following results: CO (carbon monoxide) 2.13g/kmn; WO 01/53437 PCT/SE01/00040 HC (hydrocarbons) 0.280g/km; NOx (nitrogen oxides) 0.265g/km; C0 2 (carbon dioxide) 227.0g/km; NMHC* 0.276g/km; Fuel consumption, Fe 1/100km 9.84 *Non-methane hydrocarbons.
The comparative fuel 1-7 contained A95 winter gasoline and ethanol, and had the following properties for the various compositions: Ethanol 95 5 by volume DVPE 94.9 kPa MON) 91.6 Ethanol 90 10 by volume (referred to as RFM 1 below) DVPE 94.5 kPa MON) 92.4 The testing of the reference fuel mixture (RFM1) demonstrated the following results, as compared to the winter A95 gasoline: CO -15.0%; HC NOx +15.5%;
CO
2 NMHC* Fuel consumption, F
C
1/100km +4.7% represents a reduction in emission, while represents an increase in emission.
The inventive fuel 1-8 contained A95 winter gasoline ethanol and the oxygencontaining additives and had the following properties for the various compositions: WO 01/53437 WO 0153437PCT/SE01/00040 26 A9 5 Ethanol Dilsoamyl ether =86 :8 :6 by volume DVPE 87.5 kPa, MON) 90.6 Ethanol Isobutyl acetate 88: 5 :7 by volume DVPE 87.5 kPa MON) 91.85 A95 Ethanol: Isoamyipropionate 88: 5: 7 by volume DVPE 87.0 kPa MON) 91.35 Ethanol Isoamylacetate =88: 5 7 by volume DVPE =87.5SkPa MON) 91.25 Ethanol 2-octanone 88 5 7 by volume DVPE 87.0 kPa 0.5(RON MON) 90.5 Ethanol Tetrahydrofurfuryl alcohol =88 5 7 by volume DVPE 87.5 kPa MON) 90.6 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
Ethanol Diisoamyl ether 87 9 4 by volume DVPE 90.0 kPa 0.59(RON MON) 91.0 WO 01/53437 PTSO/04 PCT/SE01/00040 27 Ethanol: Isoamyl acetate 88: 7: 5 by volume DVPE =90.0 kPa MON) 91.3 A9 5 :Ethanol: Tetrahydrofurfuryl alcohol 88 :7 5 by volume DVPE 90.0 kPa MON) 90.8 The fuel 1-9 contained A95 winter gasoline ethanol the oxygen-containing additives and 06-012 hydrocarbons and had the following properties for the various compositions: Ethanol: Isoamyl alcohol Alcylate =83.7 5: 2 9.3 by volume The boiling temperature of the alkylate is l00-130*C DVPE =88.0 kPa MON) 91.65 Ethanol Isoamyl alcohol Naphtha 83.7 5: 2: 9.3% by vol.
The boiling temperature of the naphtha is 100-200 0
C
DVPE =88.5 kPa MON) =90.8 :Ethanol :Isobutyl acetate :Alkylate 81 5 :5 :9 by volume The boiling temperature of the a lkylate is 100- 130 0
C
DVPE =87.0 kPa MON) 92.0 Ethanol Isobutyl acetate: Naphtha 81 5 5: 9 by volume The boiling temperature of the naphtha is 100-200'C DVPE =87.5 kPa MON) 91.1 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level WO 01/53437 PCT/SE01/00040 28 of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the winter gasoline is 90 kPa.
A95 Ethanol: Isoamyl alcohol Xylene 80 9.5 0.5 10 by volume DVPE 90.0 kPa MON) 92.1 Ethanol Isobutanol Isoamyl alcohol Naphtha 80 9.2 0.2 0.6 10% by volume The boiling temperature of the naphtha is 100-2000C DVPE 90.0 kPa MON) 91.0 A95: Ethanol: Isobutanol: Isoamyl alcohol: Naphtha Alkylate 80 9.2 0.2 0.6 5 5 by volume The boiling temperature of the naphtha is 100-200°C.
The boiling point of the alkylate is 100-130°C.
DVPE 90.0 kPa 0.5(RON MON) 91.6 The motor fuel compositions below demonstrate that it might be necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol below the level of DVPE of the source gasoline. Normally, this is required when DVPE of the source gasoline is higher than the limits of the regulations in force for the corresponding gasoline. In this way, for example, it is possible to transform the winter grade gasoline into the summer grade gasoline. The DVPE level for the summer gasoline is kPa.
A95 Ethanol Isobutanol Isoamyl alcohol: Naphtha Isooctane 60 9.2 0.2: 0.6 15 15 by volume The boiling temperature of the naphtha is 100-200 0
C.
DVPE 70.0 kPa MON) 91.8 WO 01/53437 PCT/SE01/00040 29 Ethanol Tert-butyl acetate Naphtha 60 9 1 30 by volume The boiling temperature of the naphtha is 100-2000C.
DVPE 70.0 kPa 0.5(RON MON) 90.4 The fuel 1-10 contains 75 by volume A95 winter gasoline, 9.6 by volume ethanol, 0.4 by volume isobutyl alcohol, 4.5 by volume m-isopropyl toluene and 10.5 by volume naphtha with boiling temperature of 100-200°C. This fuel formulation demonstrates the possibility of decreasing the DVPE, increasing the octane number, decreasing the level of toxic emissions in the exhaust and decreasing the fuel consumption in comparison with the reference mixture of gasoline and ethanol (RFM The motor fuel composition has the following properties: density at 15 0 C, according to ASTM D 4052 initial boiling point, according to ASTM D 86 vaporizable portion 70°C vaporizable portion 100"C vaporizable portion 150"C vaporizable portion 180"C final boiling point evaporation residue loss by evaporation oxygen content, according to ASTM D4815 acidity, according to ASTM D1613 weight% HAc pH, according to ASTM D1287 sulfur content, according to ASTM D 5453 gum content, according to ASTM D381 water content, according to ASTM D6304 aromatics, according to SS 155120, including benzene benzene alone, according to EN 238 DVPE, according to ASTM D 5191 749.2 kg /m3; 29*C; 47.6 by volume; 55.6 by volume; 84.2 by volume; 97.5 by volume; 194.9*C; 1.3 by volume; 1.6 by volume; 3.7%w/w; 0.004; 6.6; 18mg/kg; 1 mg/100ml; 0.03% w/w; 30.2 by volume; 0.7 by volume; 89.0kPa; WO 01/53437 PCT/SE01/00040 anti-knock index 0.5(RON+MON), according to ASTM D 2699-86 and ASTM D 2700-86 92.6 The motor fuel formulation 1-10 was tested in accordance with the standard test method EU 2000 NEDC EC 98/69 and the following results, as compared to winter gasoline, were obtained: CO -21%; HC NOx +12.8%; C02 +2.38%; NMHC Fuel consumption, Fc 1/100km +3.2% The fuel formulations 1-1 to 1-10 showed reduced DVPE over the tested ethanolcontaining motor fuels based on summer grade gasoline. Similar results are obtained when other oxygen-containing compounds of this invention are substituted for the additives of the examples 1-1 to 1-10.
To prepare the above fuel formulations 1-1 to 1-10 of this motor fuel composition, initially gasoline was mixed with ethanol and the corresponding oxygen-containing additive was added to the fuel mixture. The motor fuel composition obtained was then allowed to stand before testing between 1 and 24 hours at a temperature not lower than -35"C. All the above formulations were prepared without the use of any mixing devices.
It was established the possibility of employing an additive mixture of the oxygencontaining additive other than ethanol and ethanol for formulating the ethanol-containing motor fuels for standard internal combustion spark ignition engines meeting standard requirements for gasolines, both regarding vapour pressure and anti-knock stability.
The fuel compositions below demonstrate such a possibility.
WO 01/53437 PCT/SE01/00040 31 An mixture comprising 50% of ethanol and 50% of isoamyl alcohol was in different proportions mixed with winter grade gasolines, the dry vapour pressure equivalent (DVPE) of which does not exceed 90 kPa. All the resulting mixtures had the DVPE not higher than that required by the regulations for winter gasoline, namely 90 kPa.
A92 Ethanol Isoamyl alcohol 87 6.5 6.5 by volume DVPE 89.0 kPa MON) 90.15 A95 Ethanol Isoamyl alcohol 86 7.0 7.0 by volume DVPE 89.3 kPa MON) 92.5 A98 Ethanol: Isoamyl alcohol 85 7.5 7.5 by volume DVPE 86.5 kPa MON) 92.9 Figure 2 shows the behavior of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content when admixing the additive mixture 2 comprising 33.3% of ethanol and 66.7% of tert-pentanol with A95 winter gasoline. Figure 2 demonstrates that varying the ethanol content in gasoline within the range from 0 to 11% does not induce an increase of the vapour pressure for these compositions higher than the requirements of the standards for DVPE of the winter grade gasolines, which is 90 kPa.
Similar DVPE behaviour was observed for A92 and A98 winter gasoline mixed with an additive mixture comprising 33.3 by volume of ethanol and 66.7 by volume of tert-pentanol.
The effect of the reduction of the vapour pressure of the ethanol-containing gasolines while increasing the ethanol content in the resulting composition from 0 to 11 by volume was also observed when part of the oxygen-containing additive was replaced by C 6
-C
1 2 hydrocarbons (component The compositions below demonstrate the effect achieved by means of the invention.
WO 01/53437 PCT/SE01/00040 32 An additive mixture comprising 40 by volume of ethanol, 10 by volume of isobutanol and 50 by volume of isopropyltoluene was mixed with winter gasoline with DVPE not higher than 90 kPa. The various compositions obtained had the following properties: A92 Ethanol: Isobutanol Isopropyltoluene 85 6 1.5 7.5 by volume DVPE 84.9 kPa MON) 93.9 A95 Ethanol: Isobutanol Isopropyltoluene 80 8 2 10 by volume DVPE 84.0 kPa MON) 94.1 A98 Ethanol: Isobutanol Isopropyltoluene 86 5.6 1.4 7 by volume DVPE 85.5 kPa MON) 93.8 Similar results were obtained when other oxygen-containing compounds and also
C
6
-C
1 2 hydrocarbons of the present invention were used in the ratio of the invention to prepare the additive mixture, which was then used for preparation of the ethanol-containing gasolines. These gasolines entirely meet the requirements for the motor fuels used in the standard spark ignition engines.
EXAMPLE 2 Example 2 demonstrates the possibility of reducing the dry vapour pressure equivalent of the ethanol-containing motor fuel for the cases when gasolines with a dry vapour pressure equivalent according to ASTM D-5191 at a level of 70 kPa (about 10 psi) are used as a hydrocarbon base.
To prepare the mixtures of this composition summer gasolines A92, A95 and A98 presently sold on the market and purchased in Sweden from Shell, Statoil, and Preem, were used.
WO 01/53437 PCT/SE01/00040 33 The source gasoline comprised aliphatic and alicyclic C 4
-C
1 2 hydrocarbons, including saturated and unsaturated ones.
Figure 1 shows the behaviour of the DVPE of the ethanol-containing motor fuel based on summer A95 gasoline. The ethanol-containing motor fuels based on winter A 92 and A98 gasolines, respectively, demonstrated similar behaviour.
The following fuels 2-2 and 2-3 demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing motor fuel based on summer A92 gasoline.
The summer A92 gasoline had the following properties: DVPE 70,0 kPa Anti-knock index 0.5(RON MON)=87.5 The comparative fuel 2-1 contained A92 summer gasoline and ethanol, and had the following properties for the various compositions: A92 Ethanol 95 5 by volume DVPE 77.0 kPa MON) 89.3 A92 Ethanol 90 10 by volume DVPE 76.5 kPa 0.5(RON MON) 90.5 The fuel 2-2 contained A92 summer gasoline ethanol and the oxygencontaining additives and had the following properties for the various compositions: A92 Ethanol: Isoamyl alcohol 85 6.5 6.5 by volume DVPE 69.8 kPa MON) 90.3 A92 Ethanol Isobutanol 80 10 10 by volume WO 01/53437 PTSOIO4 PCT/SE01/00040 34 DVPE =67.5 kPa MON) =90.8 A92: Ethanol: Diethylcarbinol =85: 6.5: 6.5 by volume DVPE =69.6 kPa MON) 90.5 A92 Ethanol Diisobutyl ketone =85.5 7.5 7 by volume DVPE =69.0 kPa MON) 90.0 A92 Ethanol: Diisobutyl ethter 85: 8: 7 by volume DVPE =68.9 kPa 0.5(RON MON) 90.1 A92 Ethanol Di-.n-butyl ester 85: 8: 7 by volume DVPE =68.5 kPa.
MON) 88.5 A92 Ethanol: Isobutylacetate 88 5 :7 by volume DVPE 69.5 kPa MON) 89.5 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
A92 Ethanol: Isobutanol 87.5: 10 7.5 by volume DVPE 70.0 kPa MON 90.6 A92 Ethanol Di-n-butyl ether 8 5 9 6 by volume WO 01/53437 WO 0153437PCT/SEOIOOO40 DVPE 70.0 kPa MON) 89.2 A92: Ethanol :Dilsobutyl ketone 85: 8 by volume DVPE =70.0OkPa MON) 90.4 The fuel 2-3 contained A92 summer gasoline ethanol the oxygen-containing additives and C 6
-CI
2 hydrocarbons and had the following properties for the various compositions: A92 Ethanol: Methylethyl. ketone Isooctane 9. 5: 0. 5: 10 by volume DVPE =69.0 kPa 0.5(RON MON) 91.0 A92 Ethanol Isobutanol Isooctane 80 9.5 0.5 10 by volumne DVPE 69.0 kPa MON) =91.1 A92 Ethanol Isobutanol Isononane =80 9.5 0.5 :10 by voluim e DVPE 68.8 kPa MON) 91.0 A92 Ethanol Isobutanol Isodecane 80 9.5 0.5: 10 by volume DVPE 68.5 kPa MON) =90.8 A92 Ethanol Isobutanol: Isooctene 80: 9.5: 0.5: 10 by volume DVPE =68.9 kPa MON) 91.2 A92 Ethanol Isobutanol. Toluene 80 9.5: 0.5: 10 by volume DVPE =68.5 kPa 0.5(RON +MON) -91.4 WO 01/53437 WO 0153437PCTISE01/00040 36 A92: Ethanol: Isobutanol: Naphtha =80: 9.5: 0.5: 10 by volume The boiling temperature for the naphtha is 100-2O00C DVPE 67.5 kPa 0.5(RON MON) 90.4 A92 :Ethanol Isobutanol Naphtha Toluene =80 9.5: 0.5 5 :5 by volume The boiling temperature for the naphtha is 100-200 0
C
DVPE =67.5 kPa MON) 90.9 A92 Ethanol Isobutanol: Naphtha: Isopropyltoluene =80 :9.5 5 by volume The boiling temperature for the naphtha is 100-200*C DVPE =67.5 kPa MON) 91.2 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
A92 Ethanol Isobutanol Isodecane 82.5 9.5 0.5: 7.5 by volume DVPE 70.0 kPa MON) 90.85 A92 Ethanol Isobutanol Tert-butylbenzene 82.5 9.5 0.5 7.5 by volume DVPE 70.0 kPa MON) .91.5 WO 01/53437 PCT/SE01/00040 37 A92 Ethanol Isobutanol Isoamyl alcohol Naphtha Tert-butyltoluene 82.5 9.2 0.2 0.6 5 2.5 by volume DVPE 70.0 kPa MON) 91.1 The following fuels 2-5 and 2-6 demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing motor fuel based on summer A98 gasoline.
The summer A98 gasoline had the following specification: DVPE 69,5 kPa Anti-knock index 0.5(RON MON)=92.5 The comparative fuel 2-4 contained A98 summer gasoline and ethanol, and had the following properties for the various compositions: A98 Ethanol 95 5 by volume DVPE 76.5 kPa MON) 93.3 A98 Ethanol 90 10 by volume DVPE 76.0 kPa MON) 93.7 The fuel 2-5 contained A98 summer gasoline ethanol and the oxygencontaining additives and had the following properties for the various compositions: A98 Ethanol Isobutanol 85 7.5 7.5 by volume DVPE 69.5 kPa MON) 93.5 A98 Ethanol: Diisobutyl ketone 83 9.5 7.5 by volume DVPE 69.0 kPa 0.5(RON MON) 93.9 WO 01/53437 PCT/SE 1/00040 38 A98 Ethanol: Isobutyl acetate 88 5 7 by volume DVPE 69.5 kPa MON) 93.4 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
A98 Ethanol Isobutanol 85 8 7 by volume DVPE 70.0 kPa MON) 93.7 A98 Ethanol Tert-pentanol 90 5 5 by volume DVPE 70.0 kPa MON) 93.8 The fuel 2-6 contained A98 summer gasoline ethanol the oxygen-containing additives and Ce-C 12 hydrocarbons and had the following properties for the various compositions: A98 Ethanol Isobutanol Isooctane 80 9.5 0.5 10 by volume DVPE 69.0 kPa MON) 93.7 A98 Ethanol Isopropanol Alkylbenzene 80 5 5 10 by volume DVPE 68.5 kPa 0.5(RON MON) 94.0 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in WO 01/53437 PCT/SE01/00040 39 compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
A98 Ethanol Isobutanol Isooctane 81.5 9.5 0.5 8.5 by volume DVPE 70.0 kPa MON) 93.5 A98 Ethanol Tert-butanol Limonene 86 7 4 4 by volume DVPE 70.0 kPa 0.5(RON MON) 93.6 The following fuels 2-8 to 2-10 demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing motor fuel based on summer A95 gasoline.
The summer A95 gasoline had the following specification: DVPE 68,5 kPa Anti-knock index 0.5(RON MON) 89.8 The testing performed as above demonstrated for the summer A95 gasoline the following results: CO (carbon monoxide) 2.198g/km; HC (hydrocarbons) 0.245g/km; NOx (nitrogen oxides) 0.252g/km;
CO
2 (carbon dioxide) 230.0g/km; NMHC* 0.238g/km; Fuel consumption, Fe 1/100km 9.95 Non-methane hydrocarbons.
The comparative fuel 2-7 contained A95 summer gasoline and ethanol, and had the following properties for the various compositions: Ethanol 95% 5 by volume WO 01/53437 WO 0153437PCT/SEOI/00040 DVPE 75.5 kPa.
MOM) 90.9 Ethanol 90%: 10 by volume (also referred to as RFM2 below) DVPE 75.0 kPa MON) =92.25 The testing of the reference fuel mixture (RFM 2) demonstrated the following results, as compared to summer A95 gasoline: CO 1%; HC NOx C0 2 NMIHC* Fuel consumption, F, 1 /1 00km +3.6% ~~~represents a reduction in emission, while represents an increase in emission The fuel 2-8 contained A95 summer gasoline and the oxygen-containing additives and had the following properties for the various compositions: Ethanol: Isoamyl alcohol =85 7.5 7.5 by volume DVPE =68.5 kPa.
0.5(RON MOM) -92.2 Ethanol: Diisoamyl ether 86: 8: 6 by volume DVPE 66.5 kPa MON) 90.2 Ethanol isobutylacetate 88 5 :7 by volume DVPE =67.0 kPa MON) 92.0 A95 Ethanol: Tert-butanol 88 :5 :7 by volume WO 01/53437 WO 0153437PCT/SE01/00040 41 DVPE =68.4 kPa +.MON) 92.6 A9 5: Ethanol: Tert-pentanol =90: 5 5 by volume DVPE =68.5 kPa MON)J 92.2 Ethanol: Isopropanol 80: 10: 10 by volume DVPE =68.5 kPa O.5(RON MON) 92.8 Ethanol 4-methyl-2-pentanol 85 8 7 by volume DVPE 66.0 kPa MON) 91.0 Ethanol Diethyl ketone =85: 8 7 by volume DVPE 68.0 kPa MON) 92.2 A95 Ethanol Trimethylcyclohexanone 85 8 7 by volume DVPE 67.0 kPa MON) 91.8 Ethanol Methylter-tamyl ether 80 8: 12 by volume DVPE =68.0OkPa MON) 93.8 Ethanol n-Butylacetate =87: 6.5: 6.5 by volume DVPE 68.0 kPa 0.5(RON +i MON) 90.1 Ethanol Isobutylisobutyrate 90: 5 5 by volume DVPE =68.5 kPa MON) 90.0 WO 01/53437 PCT/SE01/00040 42 Ethanol Methylacetoacetate 85 7 8 by volume DVPE 68.5 kPa MON) 89.9 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
Ethanol: 4-methyl-2-pentanol 85 10 5 by volume DVPE 70.0 kPa 0.5(RON MON) 91.6 Ethanol Isobutylisobutyrate 90 6 4 by volume DVPE 70.0 kPa MON) 90.5 The fuel 2-9 contained A95 summer gasoline ethanol the oxygen-containing additives and C 6
-C
1 2 hydrocarbons and had the following properties for the various compositions: A95 Ethanol Tert-pentanol: Alkylbenzene 80 7 4 9 by volume DVPE 67.5 kPa MON) 93.6 Ethanol Tert-butanol: Alkylbenzene 80 7 4 9 by volume DVPE 68.0 kPa MON) 93.8 Ethanol Propanol Xylene 80 9.5 0.5 10 by volume DVPE 68.0 kPa 0.5(RON MON) 93.1 WO 01/53437 WO 0153437PCTSE01IOOO4O 43 Ethanol: Diethylketone: Xylene 80: 9.5: 0.5: 10 by volume DVPE 68.0 kPa MON) 93.2 :Ethanol: Isobutanol Naphtha: Isopropyltoluene =80 :9.5 5 by volume The boiling temperature for the naphtha is 100- 170*C DVPE =68.0 kPa 0.5(RON MON) 92.4 :Ethanol: Isobutanol Naphtha :Alkylate 80 :9.5 0.5 5 by volume The boiling temperature for the naphtha is 100- 170*C The boiling temperature for the alkylate is 100- 130*C DVPE 68.5 kPa MON) 92.2 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the summer gasoline is 70 kPa.
A95 :Ethanol: Isobutanol Isoamyl alcohol Xylene 82.5 9.2 0.2 0.6: by volume DVPE =70.0 kPa MON) 93.0 A95 Ethanol Isobutanol Isoamyl alcohol Cyclooctadiene =82.5 9.2 0.2: :0.6 7.5 %by volume DVPE 70.0 kPa MON) 92.1 WO 01/53437 PCT/SEOI/00040 44 The fuel formulation 2-10 contained 81.5% by volume of A95 summer gasoline, by volume of m-isopropyltoluene, 9.2% by volume of ethanol, and 0.8% by volume of isoamyl alcohol. Formulation 2-10 was tested to demonstrate how the inventive composition maintained the dry vapour pressure equivalent at a same level as the source gasoline while increasing the octane number, while decreasing the level of toxic emissions in the exhaust and decreasing the fuel consumption in comparison with the mixture RFM 2 of gasoline and ethanol. Formulation 2-10 had the following specific properties: density at 150C, according to ASTM D4052 initial boiling point, according to ASTM D 86 vaporisable portion 700C vaporisable portion 1000C vaporisable portion 1500C vaporisable portion 1800C final boiling point evaporation residue loss by evaporation oxygen content, according to ASTM D4815 acidity, according to ASTM D1613 weight% HAc pH, according to ASTM D1287 sulfur content, according to ASTM D 5453 gum content, according to ASTM D381 water content, according to ASTM D6304 aromatics, according to SS 155120, including benzene benzene alone, according to EN 238 DVPE, according to ASTM D 5191 anti-knock index 0.5(RON+MON), according to ASTM D 2699-86 and ASTM D 2700-86 754. lkg /m3; 26.6°C; 45.2 by volume; 56.4 by volume; 88.8 by volume; 97.6 by volume; 186.3°C; 1.6 by volume; 0.1 by volume; 3.56% w/w; 0.007; 8.9; 16mg/kg; 1mg/ 00ml; 0.12% w/w; 30.3 by volume; 0.8 by volume; 68.5kPa; 92.7 WO 01/53437 PCT/SE01/00040 The motor fuel Formulation 2-10 was tested in accordance with test method EU 2000 NEDC EC 98/69 as above and gave the following results in comparison or with the results for the source A95 summer gasoline: CO -0.18% HC NOx CO2 NMHC Fuel consumption, Fc, I/1001km +3.1% The fuel formulations 2-1 to .2-10 showed reduced DVPE over the tested ethanolcontaining motor fuels based on summer grade gasoline. Similar results are obtained when other oxygen-containing additives of the invention are substituted for the additives of the examples 2-1 to 2-10.
To prepare all the above fuel formulations 2-1 to 2-10 of this motor fuel composition, initially gasoline was mixed with ethanol, to which mixture was- then added the corresponding oxygen-containing additive. The motor fuel composition obtained was then allowed to stand before testing between 1 and 24 hours at a temperature not lower than -35*C. All the above formulations were prepared without the use of any mixing devices.
The use of an additive mixture comprising ethanol and oxygen-containing compounds other than ethanol for preparation of the ethanol-containing gasolines was accomplished with summer grade gasolines. The fuel compositions below demonstrate the possibility of obtaining the ethanol-containing gasolines to meet standard requirements for summer grade gasolines, including vapour pressure of not higher than 70 kPa.
Figure 2 shows the behaviour of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content when mixing summer A95 gasoline with the additive mixture 3 comprising 35 by volume of ethanol 5 by volume of isoamyl alcohol, and 60 by volume of naphtha boiling at temperatures between 100-170°C.
WO 01/53437 PCT/SE01/00040 46 Figure 2 demonstrates that varying the ethanol content in gasoline within the range from 0 to 20% does not induce an increase of the vapour pressure for these compositions higher than the requirements of the standards for DVPE of the summer grade gasolines, which is 70 kPa.
Similar DVPE behaviour was observed for A92 and A98 summer gasoline mixed with an additive mixture comprising 35 by volume of ethanol, 5 by volume of isoamyl alcohol, and 60 by volume of naphtha boiling at 100-170C.
The ratio between ethanol and the oxygen-containing compound other than ethanol in the additive mixture, which is used for preparation of the ethanol-containing gasolines, is of substantial importance. The ratio between the components of the additive established by the present invention enables to adjust the vapour pressure of the ethanol-containing gasolines over a wide range.
The compositions below demonstrate the possibility of employing the additive mixtures with both high and low ethanol content. An additive mixture comprising 92 by volume of ethanol, 6 by volume of isoamylalcohol, and 2 by volume of isobutanol was mixed with summer grade gasoline. The compositions obtained had the following properties: A92 Ethanol Isoamyl alcohol Isobutanol 80 18.4 1.2 0.4 by volume DVPE 70.0 kPa 0.5(RON MON) 90.3 Ethanol Isoamyl alcohol Isobutanol 82 16.56 1.08 0.36 by volume DVPE 69.9 kPa 0.5(RON MON) 92.6 A98 Ethanol Isoamyl alcohol Isobutanol 78 20.24 1.32 0.44 by volume DVPE 70.0 kPa WO 01/53437 PCT/SE01/00040 47 MON) 94.5 An additive mixture comprising 25 by volume of ethanol, 60 by volume of isoamyl alcohol, and 15 by volume of isobutanol was mixed with summer grade gasoline. The compositions obtained had the following properties: A92 Ethanol Isoamyl alcohol Isobutanol 80 5 12 3 by volume DVPE 66.0 kPa MON) 88.6 Ethanol Isoamyl alcohol Isobutanol 84 4 9.6 2.4 by volume DVPE 65.5 kPa MON) 91.3 A98 Ethanol Isoamyl alcohol Isobutanol 86 3.5 8.4 2.1 by volume DVPE 65.0 kPa MON) 93.0 Similar results were obtained when other oxygen-containing compounds and also C 6
-C
12 hydrocarbons of this invention were used in the ratio established by this invention to prepare the additive mixture, which was then used for preparation of the ethanol-containing gasolines. These gasolines entirely meet the requirements for the motor fuels used in the standard spark ignition engines.
Moreover, the additive mixture comprising ethanol and the oxygen-containing compound of this invention other than ethanol with the ratio of the present invention can be used as an independent motor fuel for the engines adapted for operation on ethanol.
EXAMPLE 3 Example 3 demonstrates the possibility of reducing the dry vapour pressure equivalent of the ethanol-containing motor fuel for the cases when gasolines with WO 01/53437 PCT/SE01/00040 48 dry vapour pressure equivalent according to ASTM D-5191 at a level of 48 kPa (about 7 pSi) are used as the hydrocarbon base.
To prepare the mixtures of this composition lead-free summer gasolines A92, and A98 meeting US standards and purchased in the USA under the trademarks Phillips J Base Fuel, Union Clear Base and Indolene, were used.
The source gasolines comprised aliphatic and alicyclic Cs-C 12 hydrocarbons, including both saturated and unsaturated ones.
Fig. 1 shows the behaviour of the DVPE of the ethanol-containing motor fuel based on US summer grade A92 gasoline. The ethanol-containing motor fuels based on US summer A95 and A98 gasolines, respectively, demonstrated similar behaviour.
The US summer A92 gasoline had the following specification: DVPE 47,8 kPa Anti-knock index 0.5(RON MON)=87.7 The fuel 3-1 contained US A92 summer gasoline and ethanol and had the following properties for the various compositions: A92 Ethanol 95 5 by volume DVPE 55.9 kPa MON) 89.0 A92 Ethanol =90 10 by volume DVPE 55.4 kPa MON) 90.1 The fuel 3-2 contained US A92 summer gasoline, ethanol, and the oxygencontaining additives and had the following properties for the various compositions: A92 Ethanol: Isoamyl alcohol 83 8.5 8.5 by volume DVPE 47.5 kPa MON) 89.6 WO 01/53437 WO 0153437PCU/SE01/00040 49 A92: Ethanol: Isoamyl propionate 82: 8: 10 by volume DVPE =47.0 kPa MON) =89.9 A92 Ethanol 2-Ethyihexanol 82 8: 10 by volume DVPE =47.8 kPa MON) =89.2 A92 Ethanol Tetrahydrofurfuryl alcohol =82 7 :10 by volume DVPE =47.8 kPa MON) 89.3 A92 Ethanol: Cyclohexanone 82 10 by volume DVPE 47.7 kPa 0.5(RON MON) 89.1 A92 Ethanol Methoxybenzene 80 8.5: 11.5 by volume DVPE 46.8 kPa MON) 90.6 A92 Ethanol: Methoxytoluene 82 8: 10 by volume DVPE =46.5 kPa MON) 90.8 A92 Ethanol Methylbenzoate 82 8: 10 by volume DVPE =46.0 kPa MON) 90.5 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of the DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the US summer grade gasoline is 7 psi, which corresponds to 48.28 kPa.
WO 01/53437 WO 0153437PCTSE1OOO40 A92 :Ethanol Isoamyl alcohol 83 9 8 by volume DVPE 48.2 kPa.
MON) 89.8 A92 Ethanol: Methoxytoluene 84: 8 8 by volume DVPE 48.2 kPa.
MON) 90.5 A92: Ethanol: Methylbenzoate =85: 8: 7 by volume DVPE =48.2 kPa.
MON) 90.1 The fuel 3-3 contained US A92 summer gasoline ethanol the oxygencontaining additives and C 6
-C
12 hydrocarbons and had the following properties for the various compositions: A92 :Ethanol Isoamyl alcohol Isobutyl alcohol :Naphtha 75 :9.2 :0.3: 0.1: 15.4 by volume The boiling temperature for the naphtha is 100-200*C DVPE =47.8 kPa.
MON) =89.5 A92 Ethanol: Isoamyl alcohol Isobutyl alcohol m-Isopropyltoluene 9.2: 0.3 :0.1 15.4 by volume DVPE =47.0QkPa MON) 90.5 A92 :Ethanol Isoamyl alcohol Isobutyl alcohol Isooctane 75 9.2 :0.3: 0.1: 15.4 by volume DXPE =47.8 kPa MON) 90.3 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the WO 01/53437 PCT/SE01/00040 51 level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the US summer grade gasoline is 7 psi, which corresponds to 48.28 kPa.
A92 Ethanol Isoamyl alcohol Isobutyl alcohol Naphtha 76 9.2 0.3 0.1 14.4 by volume The boiling temperature for the naphtha is 100-200 0
C
DVPE 48.2 kPa 0.5(RON MON) 89.6 A92 Ethanol Isoamyl alcohol Isobutyl alcohol Naphtha Isooctane 76 9.2 0.3 0.1 10.4 4 by volume The boiling temperature for the naphtha is 100-200°C DVPE 48.2 kPa MON) 89.8 A92 Ethanol Isoamyl alcohol Isobutyl alcohol Naphtha m-Isopropyl toluene 77 9.2 0.3 0.1 10.4 3 by volume The boiling temperature for the naphtha is 100-200°C DVPE 48.2 kPa MON) 89.9 The following fuels demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing motor fuel based on US A98 summer gasoline.
The US A98 gasoline had the following specification: DVPE 48.2 kPa Anti-knock index 0.5(RON MON)= 92.2 The comparative fuel 3-4 contained US A98 summer gasoline and ethanol and had the following properties for the various compositions: WO 01/53437 WO 0153437PCT/SEOI/00040 52 A98 Ethanol 95: 5 by volumne DVPE 56.3 kPa MON) 93.0 A98 :Ethanol 90 10 by volume DVPE 55.8 kPa O.S(RON MON) 93.6 The fuel 3-5 contained US A98 sumrmer gasoline ethanol and the oxygencontaining additives and had the following properties for the various compositions: A98 Ethanol: Isoamyl alcohol 82.5 9 :8.5 by volume DVPE 48.2 kPa 0.5(RON MON) 93.3 A98 :Ethanol :Isoamyl alcohol Isobutyl alcohol 82.5 9 7 1.5 by volume DVPE =48.2 kPa 0.5(RON MON) 93.4 A98 Ethanol Tetrahydrofurfuryl alcohol 80 10 10 by volume DVPE 48.0 kPa MON) 93.7 The fuel 3-6 contained US A98 summer gasoline ethanol the oxygencontaining additives and C6-CI 2 hydrocarbons and had the following properties for the various compositions: A98 :Ethanol: Isoamyl alcohol Isobutyl. alcohol Naphtha 75 9.2 0.3: 0.1 :15.4 by volume The boiling temperature for the naphtha is 10-200*C DVPE =48.2 kPa MON) =93.3 WO 01/53437 WO 0153437PCT/SE01/00040 53 A98 Ethanol: Isoamyi alcohol: Isobutyl alcohol: Isooctane 75 9.2 :0.3 0.1: 15.4 by volume DVPE 48.2 kPa 0.5(RON MON) 93.9 A98 Ethanol Isoaniyl alcohol Isobutyl alcohol: m-Isopropyltoluene 75.5 9.2: 0.3 :0.1 14.9 by volume DVPE 47.5 kPa 0.5(RON MON) 94.4 A98 Ethanol: Isoamyl alcohol Isobutyl alcohol Naphtha :Isooctane 9.2: 0.3: :0.1 7% by volumie The boiling temperature for the naphtha is 100-200'C DVPE =48.2 kPa MON) 93.6 A98 Ethanol Isoamyl alcohol Isbbutyl alcohol Naphtha: m-Isopropyl toluene =75 0.1 :10.4: 5 %byvolumne The boiling temperature for the naphtha is 100-200*C DVPE =48.0 kPA MON) =93.7 A98 Ethanol soamyl alcohol Isobutyl alcohol Naphtha: Alkylate 9.2: 0.3: :0.1 7.5 by volume The boiling temperature for the naphtha is 100-200'C.
The boiling temperature for the alkylate is 100-130*C.
DVPE 48.2 kPa MON) =93.6 The following fuels demonstrated the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing motor fuel based on US summer gasoline.
WO 01/53437 PCT/SE01/00040 54 The US summer A95 gasoline had the following specification: DVPE 47.0 kPa Anti-knock index 0.5(RON MON) 90.9 The US summer A95 gasoline was used as a reference fuel for the testing performed according to EU2000 NEDC EC 98/69 test cycle on a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No. LG4F20-87) developing 83 kW at 90 revolutions/second and a torque of 185 Nm at 46 revolutions/second.
The testing performed as above demonstrated for the US summer A95 gasoline the following results: CO (carbon monoxide) 2.406g/km; HC (hydrocarbons) 0.356g/km; NOx (nitrogen oxides) 0.278g/km; CO2 (carbon dioxide) 232.6g/km; NMHC* 0.258g/km; Fuel consumption, Fc 1/100km 9.93 Non-methane hydrocarbons.
The comparative fuel 3-7 contained US A95 summer gasoline and ethanol and had the following properties for the various compositions: A95 Ethanol 95 5 by volume DVPE 55.3 kPa MON) 91.5 Ethanol 90 10 by volume DVPE 54.8 kPa MON) 92.0 Testing of the reference gasoline-alcohol mixture (RFM3) comprising 90 by volume of US A95 summer grade gasoline and 10 by volume of ethanol performed on WO 01/53437 WO 0153437PCT/SE01100040 a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No. LG4F2O-87) in accordance with the standard test method EU 2000 NEDC EC 98/69 demonstrated the following results, as compared to summer US A95 gasoline: CO 12.5%; HC NOx 002 NMHC* Fuel consumption, F, 1/ 1001km +3.1% t-.represents a reduction in emission, while represents an increase in emission.
The' fuel 3-8 contained US A95 summer gasoline, ethanol and the oxygencontaining additives, and had the following properties for the various compositions: Ethanol: Isoamyi alcohol =83 8.5 8.5 by volume DVPE 47.0 kPa MON) 91.7 Ethanol: n-Amyl acetate =80: 10: 10 by volume DVPE 47.0 kPa MON) 91.8 A9 5 Ethanol Cyclohexylacetate 80 :10 10 by volume DVPE 46.7 kPa MON) 92.0 Ethanol Tetramethyltetrahydrofurane =8 0 :12 8 by volume DVPE =47.0OkPa MON) 92.6 Ethanol: Methyltetrahydropyrane 80: 15 5 by volume DVPE 46.8 kPa WO 01/53437 PCT/SE01/00040 56 MON) 92.5 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the US summer grade gasoline is 7 psi, which corresponds to 48.28 kPa.
A95 Ethanol Isoamyl alcohol 84 8.5 7.5 by volume DVPE 48.2 kPa MON) 91.7 Ethanol: Phenylacetate 82.5 10 7.5 by volume DVPE 48.2 kPa MON) 92.3 Ethanol Tetramethyltetrahydrofurane 81 10 9 by volume DVPE 48.2 kPa 0.5(RON MON) 92.2 The fuel 3-9 contained US A95 summer gasoline ethanol the oxygencontaining additives and C6-C12 hydrocarbons and had the following properties for the various compositions: Ethanol: Isoamyl alcohol Isobutyl alcohol Naphtha 75 9.2 0.3 0.1 15.4 by volume The boiling temperature for the naphtha is 100-200°C DVPE 47.0 kPa 0.5(RON MON) 91.6 Ethanol: Isoamyl alcohol Isobutyl alcohol: Isooctane 75 9.2 0.3 0.1 15.4 by volume DVPE 47.0 kPa WO 01/53437 WO 0153437PCTISEO1/00040 57 MON) =92.2 Ethanol :Isoamiyl alcohol: Isobutyl alcohol: m-Isopropyltoluene 9.2: 0.3 0.1: 15.4 by volume DVPE =46.8 kPa MON) =93.0 Ethanol Tetrahydrofurftiryl alcohol: Cyclooctatetraene =80 9.5 %by volume DVPE =46.6 kPa.
MON) 92.5 Ethanol 4-Methyl-4-oxytetrahydropyrane Allocymene =80 10 by volume DVPE =46.7 kPa MON) =92.1 The motor fuel compositions below demonstrate that it is not always necessary to reduce the excess DVPE of the motor fuel caused by the presence of ethanol to the level of DVPE of the source gasoline. In some cases it is sufficient just to bring it in compliance with the requirements of the regulations in force for the corresponding gasoline. The DVPE level for the US summer grade gasoline is 7 pSi, which corresponds to 48.28 kPa.
A95 Ethanol: Isoamyl alcohol: Isobutyl alcohol Naphtha 76.5 9.2: 0.3 1 7: 6,9 by volumne The boiling temperature for the naphtha is 100-200oC.
DVPE 48.2 kPa MON) 91.7 Ethanol Isoamyl alcohol Isobutyl alcohol Naphtha :Isooctane 76.5: 9.2: 0.3: 0.1: 6.9 by volume The boiling temperature for the naphtha is 100-200'C.
DVPE 48.2 kPa WO 01/53437 PCT/SE01/00040 MON) 92.2 Ethanol Isoamyl alcohol Isobutyl alcohol m-Isopropyltoluene 77 9.2 0.3 0.1 13.4 by volume DVPE 48.2 kPa MON) 92.9 The fuel formulation 3-10 contained 76 by volume of US A95 summer gasoline, 9.2 by volume of ethanol, 0.25 by volume of isoamyl alcohol, 0.05 by volume of isobutyl alcohol, 11.5 by volume of naphtha with boiling temperature of 100- 200 0 C, and 3 by volume of isopropyltoluene. Formulation 3-10 was tested to demonstrate how the invention enables the production of ethanol-containing gasoline entirely meeting the requirements of the standards in force, firstly for the level of the DVPE and also for the other parameters. At the same time this gasoline secures a decrease of toxic emissions in the exhaust and lower fuel consumption in comparison to the mixture RFM 3 of source US A95 summer gasoline with 10% of ethanol. Formulation 3-10 had the following specific properties: density at 15°C, according to ASTM D4052 initial boiling point, according to ASTM D 86 vaporisable portion 70"C vaporisable portion 100°C vaporisable portion 150°C vaporisable portion 190°C final boiling point evaporation residue loss by evaporation oxygen content, according to ASTM D4815 acidity, according to ASTM D1613 weight% HAc pH, according to ASTM D1287 774.9kg /m3; 36.1C; 33.6 by volume; 50.8 by volume; 86.1 by volume; 97.0 by volume; 204.8*C; 1.5 by volume; 1.5 by volume; 3.37% w/w; 0.007; 7.58; WO 01/53437 PCT/SE01/00040 sulfur content, according to ASTM D 5453 gum content, according to ASTM D381 water content, according to ASTM D6304 aromatics, according to SS 155120, including benzene benzene alone, according to EN 238 DVPE, according to ASTM D 5191 anti-knock index 0.5(RON+MON), according to ASTM D 2699-86 and ASTM D 2700-86 47mg/kg; 2.8mg/100ml; 0.02% w/w; 31.2 by volume; 0.7 by volume; 48.0kPa; 92.2 The motor fuel Formulation 3-10 was tested on a 1987 Volvo 240 DL with a B230F, 4cylinder, 2.32 litre engine (No. LG4F20-87) in accordance with test method EU 2000 NEDC EC 98/69 as above and gave the following results in comparison or with the results for the source US A95 summer gasoline:
CO
HC
NOx C02
NMHC
Fuel consumption, Fc, I/100km -15.1% unchanged; unchanged.
Similar results were obtained when the other oxygen-containing compounds substituted the tested oxygen-containing compounds.
To prepare all the fuel formulations above, initially US summer gasoline was mixed with ethanol, to which mixture was then added the corresponding oxygencontaining additive. The motor fuel composition obtained was then allowed to stand before testing between 1 and 24 hours at a temperature not lower than -35*C. All the above formulations were prepared without the use of any mixing devices.
It was established the possibility of employing of the additive mixture comprising ethanol and oxygen-containing compounds other than ethanol also for adjustment of the vapour pressure of the ethanol-containing motor fuels used in standard in- WO 01/53437 PCT/SE01/00040 ternal combustion spark ignition engines based on summer grade gasolines meeting US standards. Adding Cs-C 1 2 hydrocarbons to the composition of the additive mixture increased the efficiency of the vapour pressure reducing impact of the additive on the excess vapour pressure caused by presence in the gasoline of ethanol.
The additive mixture comprising 60 by volume of ethanol, 32 by volume of isoamyl alcohol and 8 by volume of isobutyl alcohol was in different proportions mixed with US summer grade gasolines having dry vapour pressure equivalent (DVPE) not higher than 7 psi, which corresponds 48.28 kPa.
The compositions obtained had the following properties: A92 Ethanol Isoamyl alcohol: Isobutanol 87.5 7.5 4 1 by volume DVPE 51.7 kPa 0.5(RON MON) 89.7 Ethanol Isoamyl alcohol: Isobutanol 85 9 4.8 1.2 by volume DVPE 51.0 kPa MON) 91.8 A98 Ethanol Isoamyl alcohol: Isobutanol 80 12 6.4 1.6 by volume DVPE 52.0 kPa MON) 93.5 The foregoing examples demonstrate the possibility of partially lowering the excess vapour pressure, by about 50% of the excess vapour pressure of gasoline induced by the presence of ethanol in the mixture.
An additive mixture comprising 50 by volume of ethanol and 50 by volume of methylisobutyl ketone was mixed in different proportions with US summer grade gasoline with dry vapour pressure equivalent (DVPE) not higher than 7 psi, which corresponds to 48.28 kPa. The compositions obtained had the following properties: A92 Ethanol Methylisobutyl ketone 85 7.5 7.5 by volume DVPE 49.4 kPa WO 01/53437 PCT/SE01/00040 61 MON) 90.0 Ethanol Methylisobutyl ketone 84 8 8 by volume DVPE 48.6 kPa 0.5(RON MON) 91.7 A98 Ethanol Methylisobutyl ketone 82 9 9 by volume DVPE 49.7 kPa MON) 93.9 The foregoing examples demonstrate the possibility of a partial lowering of the excess vapour pressure by about 80% of the excess vapour pressure of gasoline induced by the presence of ethanol in the mixture.
Figure 2 shows the behaviour of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content in the mixtures of US summer A92 gasoline and the additive mixture 4 comprising 35 by volume of ethanol, 1 by volume of isoamyl alcohol, 0.2 by volume of isobutanol, 43.8 by volume of naphtha boiling at temperatures between 100-170 0 C, and 20% of isopropyl toluene.
Figure 2 demonstrates that employment of this additive mixture in formulation of ethanol-containing gasoline enables the reduction of more than 100% of the excess vapour pressure induced by the presence of ethanol.
Similar results for DVPE were obtained for US summer grade A95 and A98 gasoline mixed with the additive mixture composed of 35 by volume of ethanol, 1 by volume of isoamyl alcohol, 0.2 by volume of isobutanol, 43.8 by volume of naphtha boiling at 100-170 0 C and 20% by volyme of isopropyltoluene.
Similar results were obtained when other oxygen-containing compounds and C6-C 1 2 hydrocarbons of this invention were used in the proportion established by this invention to formulate the additive mixture, which was then used for preparation of the ethanol-containing gasolines. These gasolines entirely meet the requirements for the motor fuels used in standard internal combustion spark ignition engines.
WO 01/53437 PCT/SE01/00040 62 Moreover, the additive mixture comprising ethanol, the oxygen-containing compound other than ethanol, and C6-C 1 2 hydrocarbons in the proportion and composition of the present invention, can be used as an independent motor fuel for the engines adopted for operation on ethanol.
EXAMPLE 4 Example 4 demonstrates the possibility of reducing the dry vapour pressure equivalent of the ethanol-containing motor fuel for the cases when the hydrocarbon base of the fuel is a non-standard gasoline with a dry vapour pressure equivalent according to ASTM D-5191 at a level of 110 kPa (about 16 psi).
To prepare the mixtures of this composition lead-free winter gasoline A92, A95, and A98 purchased in Sweden from Shell, Statoil, Q80K and Preem and gas condensate (GK) purchased in Russia from Gazprom were used.
The hydrocarbon component (HCC) for the motor fuel compositions was prepared by mixing about 85 by volume of winter A92, A95 or A98 gasoline with about by volume of gas condensate hydrocarbon liquid (GC).
To prepare the hydrocarbon component (HCC) for the fuel formulations 4-1 to 4-10 of this motor fuel composition, about 85 by volume of winter A92, A95 or A98 gasoline was first mixed with the gas condensate hydrocarbon liquid The obtained hydrocarbon component (HCC) was then allowed to stand for 24 hours. The resulting gasoline contained aliphatic and alicyclic C3-C12 hydrocarbons, including saturated and unsaturated ones.
Fig. 1 demonstrates the behaviour of the DVPE of the ethanol-containing motor fuel based on winter A98 gasoline and gas condensate. The ethanol-containing motor fuel based on winter A92 and A98 gasoline and gas condensate (GC) demonstrated similar behaviour.
Gasoline comprising 85 by volume of winter gasoline A92 and 15 by volume of gas condensate (GC) had the following properties: WO 01/53437 WO 0153437PCT/SEOI/00040 63 DVPE 110.0 kPa Anti-knock index 0.5(RON MON)=87.9 The comparative fuel 4-1 contained A92 winter gasoline, gas condensate (GC) and ethanol and had the following properties for the various compositions: A92: GCO Ethanol= 80.75: 14.25: 5 by volume DVPE 115.5 kPa MON) 89.4 A92 GO Ethanol= 76.5: 13.5: 10 by volume DVPE 115.0 kPa MON) 90.6 The inventive fuel 4-2 contained A92 winter gasoline, gas condensate ethanol and the oxygen-containing additive and had the following properties for the various compositions: A92: GC Ethanol: Isoamyl alcohol 74: 13 6.5 6.5 by volume DVPE =109.8 kPa.
MON) =90.35 A92 GCO: Ethanol: 2,5 Dimethyltetrahydrofuran =68 12 :10 :10 by volume DVPE= 110.0 kPa MON) =90.75 A92: GC: Ethanol: Propanol 68: 12: 12: 8 %by volume DXTPE 109.5 kPa 0.5(RON MON) 90.0 A92 GO Ethanol: Diisopropylcarbinol =72: 13 7.5 7.5 by volume DVPE =109.0 kPa MON) =90.3 WO 01/53437 WO 0153437PCT/SE01/00040 64 A92 :GC :Ethanol Acetophenone 72:13 :9 :6 by volume DVPE 110.0 kPa MON) 90.8 A92 GC Ethanol Isobutyipropionate =75: 13: 5 7 by volume DVPE 109.2 kPa MON) =90.0 The fuel 4-3 contained winter A92 gasoline, gas condensate ethanol, the oxygen-containing additive and 06-C12 hydrocarbons and had the following properties for the various compositions: A92 GC Ethanol :Isobutanol: Isopropylbenzene 68 12 9.5 0.5 by volume DVPE =108.5 kPa MON) 91.7 A92 GC :Ethanol Tert-butylethyl ether: Naphtha 6 8: 12 9.5 0.5 by volume The boiling temperature for the naphtha is 10-200*C.
DVPE 108.5 kPa MON) 90.6 A92 GC Ethanol :Isoamylinethyl ether Toluene =68 12 9.5 0.5 by volume DVPE =107.5 kPa MON) 91.6 The fuel compositions below demonstrate that the invention enables the reduction of the excess DVPE of the non-standard gasoline to the level of the corresponding standrd gasoline. The DVPE for the standard A92 winter gasoline is 90 kPa.
A92: GOC: Ethanol Isoamyl alcohol: Naphtha: Alkylate 55: 10 9.5 12.5: 12.5 by volume WO 01/53437 PCT/SE01/00040 The boiling temperature for the naphtha is 100-2000C.
The boiling temperature for the alkylate is 100-1300C.
DVPE 90.0 kPa MON) 90.6 A92 GC Ethanol: Isoamyl alcohol Naphtha Ethylbenzene 55 10 0.5 15 10 by volume The boiling temperature for the naphtha is 100-200°C.
DVPE 89.8 kPa 0.5(RON MON) 90.9 A92 GC Ethanol: Isoanyl alcohol: Naphtha: Isopropyltoluene 55 10 0.5 20 5 by volume The boiling temperature for the naphtha is 100-2000C.
DVPE 90.0 kPa MON) 90.6 The following compositions demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing fuel mixtures based on about 85 by volume of winter A98 gasoline and about 15 by volume of gas condensate.
The gasoline comprising 85 by volume of winter A98 gasoline and 15 by volume of gas condensate (GC) had the following specification: DVPE 109.8 kPa Anti-knock index 0.5(RON MON)=92.0 The comparative fuel 4-4 contained A98 winter gasoline, gas condensate (GC) and ethanol and had the following properties for the various compositions: A98 GC Ethanol 80.75 14.25 5 by volume DVPE 115.3 kPa MON) 93.1 WO 01/53437 WO 0153437PCT/SEOI/00040 66 A98 GC :Ethanol 76.5: 13.5: 10 by volume DVPE 114.8 kPa MON) 94.0 The inventive fuel 4-5 contained A98 winter gasoline, gas condensate (GO) and the oxygen-containing additives and had the following properties for the various compositions: A98 GC :Ethanol: Isoamyl alcohol =74 :13: 6.5 6.5 by volume DVPE =109.6 kPa MON) 93.3 A98 GC Ethanol: Ethoxybenzene 72 :13 7.5 7.5 by volume DVPE 110.0 kPa 0.5(RON MON) 94.0 A98 GO Ethanol: 3,3,5 Trimethylcyclohexanone 72 :13 7.5 7.5 by volume DVPE 109.8 kPa 0.5(RON MON) 93.3 The fuel 4-6 contained A98 winter gasoline, gas condensate, ethanol, the oxygencontaining additives, and 06-012 hydrocarbons and had the following properties for the various compositions: A98 GC Ethanol: Isoamyl alcohol Isobutyl alcohol Naphtha 68 12: 9.2: 0.6: 0.2: 10 %by volumae The boiling temperature for the naphtha is 100-200*C.
DVPE =107.4 kPa 0.5(RON MON) 93.8 A98 GO Ethanol Ethylisobutyl ether: Myrzene 72 13 9.5 0.5 5 by volume DVPE =110.0 kPa WO 01/53437 WO 0153437PCT/SE01/00040 67 MON) 93.6 A98: GC: Ethanol Isobutanol: Isooctane 68: 12: 5: 5: 10 by volume DVPE 102.5 kPa 0.5(RON MON) 93.5 The motor fuel compositions below demonstrate that the invention enables the reduction of the excess DVPE of non-standard gasoline to the level of DVPE of the corresponding standard gasoline. The DVPE for the standard winter A98 gasoline is 90.0 kPa.
A92 GC: Ethanol Isoamyl alcohol: Naphtha: Alkylate =55: 10 9.5: 12.5: 12.5 by volume The boiling temperature for the naphtha is 10-2000C.
The boiling temperature for the alkcylate is 100-130 0
C.
DVPE 89.8 kPa MON) 94.0 A92: GO Ethanol Isoamyl alcohol Naphtha Isopropylbenzene =55: 9.5:O0.5: 15: 10 %by volume The boiling temperature for the naphtha is lOO-200*C.
DVPE =89.6 kPa MON) =94.2 A9 2: GO Ethanol Isobutanol Naphtha Isopropyltoluene 55: 10 5 by volume The boiling temperature for the naphtha is 100-2000C.
DVPE 88.5 kPa MON) 94.1 The following compositions demonstrate the possibility of adjusting the dry vapour pressure equivalent (DVPE) of the ethanol-containing fuel mixtures based on about by volume of winter A95 gasoline and about 15 by volume of gas condensate.
WO 01/53437 PCT/SE01/00040 68 The gasoline comprising 85 by volume of winter A98 gasoline and 15 by volume of gas condensate (GC) had the following specification; DVPE 109.5 kPa Anti-knock index 0.5(RON MON)=90.2 The hydrocarbon component (HCC) comprising 85 by volume of winter gasoline and 15 by volume of gas condensate (GC) was used as a reference fuel for testing as described above and gave the following results: CO 2.033 g/km; HC 0.279 g/km; NOx 0.279 g/km; C02 229.5 g/km; NMHC 0.255 g/km; Fuel consumption, Fc, 1/ 100km 9.89 The fuel 4-7 contained A95 winter gasoline, gas condensate (GC) and ethanol and had the following properties for the various compositions: GC Ethanol 80.75 14.25 5 by volume DVPE 115.0 kPa MON) 91.7 A95 GC Ethanol 76.5 13.5 10 by volume DVPE 114.5 kPa MON) 92.5 The reference fuel mixture (RFM4) comprising 80.75% of winter A95 gasoline, 14.25% of gas condensate (GC) and 5% of ethanol was tested as described above and gave the following results in comparison or with the results for the gasoline comprising 85 by volume of winter gasoline A95 and 15 by volume of gas condensate (GC): CO -6.98% WO 01/53437 WO 0153437PCT/SE01/00040 69 HC NOx 12. 1%; C02 NMH-C Fuel consumption, Fc, 1/ 100kmn +2.62%.
The inventive fuel 4-8 contained A95 winter gasoline, gas condensate ethanol and the oxygen-containing additives and had the following properties for the various compositions: GO: Ethanol: Isoamyl alcohol =74: 13 6.5 by volume DVPE =109.1 kPa.
MON) 92.0 A95: GC :Ethanol: Phenol 72: 13:8: 7 %by volume DVPE 107.5 kPa.
MON) 92.6 GO Ethanol: Phenyl acetate 68: 12: 10: 10 by volume DVPE 106.0 kPa.
MON) 92.8 GOC: Ethanol: 3-Hydroxy-2-butanone =68: 12:10: 10 by volume DVPE =108.5 kPa.
0.5(RON MON) 91.6 GC Ethanol Tert-butylacetoacetate =68: 12:10 :10 by volume DVPE -108.0 kPa MON) =92.2 GO Ethanol: 3,3,5-Trimethylcyclohexanone =71 12 9 8 by volume DVPE =108.5 kPa MON) =91.6 WO 01/53437 PCT/SE01/00040 The fuel 4-9 contained A95 winter gasoline, gas condensate ethanol, the oxygen-containing additives, and C6-C 12 hydrocarbons and had the following properties for the various compositions: A95 GC Ethanol: Isoamyl alcohol Isobutyl alcohol Naphtha 68 12 9.2 0.6 0.2 10 by volume The boiling temperature for the naphtha is 100-2000C.
DVPE 107.0 kPa MON) 92.1 GC Ethanol: Isobutanol Cyclooctatetraene 72 13 9.5 0.5 5 by volume DVPE 108.5 kPa MON) 92.6 The motor fuel compositions below demonstrate that the invention enables the reduction of the excess vapour pressure equivalent (DVPE) of the non-standard gasoline to the level of the corresponding standard gasoline. The DVPE of the standard winter gasoline A95 is 90.0 kPa.
GC Ethanol: Isoamyl alcohol Isobutanol Naphtha Alkylate 55 9.2 0.6 0.2 12.5 12.5 by volume The boiling temperature for the naphtha is 100-2000C.
The boiling temperature for the alkylate is 100-1300C.
DVPE 89.5 kPa MON) 92.4 GC Ethanol: Isoamyl alcohol Naphtha Tert-butylxylene 55 10 0.5 20 5 by volume The boiling temperature for the naphtha is 100-200°C.
DVPE 89.8 kPa MON) 92.5 WO 01/53437 PCT/SE01/00040 71 GC Ethanol: Isobutanol Naphtha: Isopropylbenzene 55 10 5 20 5 by volume The boiling temperature for the naphtha is 100-2000C.
DVPE 89.9 kPa 0.5(RON MON) 92.2 The motor fuel 4-10 contained 55% by volume of A95 winter gasoline, 10% by volume of gas condensate 5% by volume of ethanol, 5% by volume of tertbutanol, 20% by volume of naphtha with boiling temperature of 100-200 0 C and by volume of isopropyltoluene. Formulation 4-10 was tested to demonstrate how the invention enables the formulation of ethanol-containing gasoline entirely meeting requirements of the standards in force, firstly in respect of the dry vapour pressure equivalent limit, and also for the other parameters of the fuel, even when the source hydrocarbon component (HCC) has a DVPE considerably higher than the requirements of the standards. At the same time this ethanol-containing gasoline decreases the level of toxic emissions in the exhaust and decreases the fuel consumption in comparison with the above-described mixture RFM 4. The formulation 4-10 had the following specific properties: density at 15°C, according to ASTM D4052 initial boiling point, according to ASTM D 86 vaporisable portion 70°C vaporisable portion 100°C vaporisable portion 150°C vaporisable portion 180°C final boiling point evaporation residue loss by evaporation oxygen content, according to ASTM D4815 acidity, according to ASTM D1613 weight% HAc 698.6 kg /m3; 20.5°C; 47.0 by volume; 65.2 by volume; 92.4 by volume; 97.3 by volume; 189.9*C; 0.5 by volume; 1.1 by volume; 3.2% w/w; 0.001; WO 01/53437 PCT/SE01/00040 pH, according to ASTM D1287 sulfur content, according to ASTM D 5453 gum content, according to ASTM D381 water content, according to ASTM D6304 aromatics, according to SS 155120, including benzene benzene alone, according to EN 238 DVPE, according to ASTM D 5191 anti-knock index 0.5(RON+MON), according to ASTM D 2699-86 and ASTM D 2700-86 18 mg/kg; 2 mg/ 100mlr; 0.01% w/w; 30.9 by volume; 0.7 by volume; 90.0 kPa; 92.3 The motor fuel Formulation 4-10 was tested as above and gave the following results in comparison or with the results for the motor fuel comprising 85 by volume of winter A95 gasoline and 15 by volume of gas condensate:
CO
HC
NOx C02
NMHC
Fuel consumption, Fc, 1/100km -14.0% unchanged; Similar results are obtained when other oxygen-containing additives of the invention are substituted for the oxygen-containing additives of the examples 4-1 to 4-10.
To prepare all the above fuel formulations 4-1 to 4-10 of this motor fuel composition, the hydrocarbon component (HCC), which is a mixture of winter gasoline and gas condensate was initially mixed with ethanol, to which mixture then was added the corresponding oxygen-containing additive and C6-C12 hydrocarbons. The motor fuel composition obtained was then allowed to stand before testing between I and 24 hours at a temperature not lower than -35"C. All the above formulations were prepared without the use of any mixing devices.
The inventive fuel formulations demonstrated the possibility of adjusting the vapour pressure of the ethanoi-ccontaining motor fuels for the standard internal combus- WO 01/53437 PCT/SE01/00040 73 tion spark ignition engines based on non-standard gasolines having a high vapour pressure.
Figure 2 shows the behaviour of the dry vapour pressure equivalent (DVPE) as a function of the ethanol content of the mixtures of the hydrocarbon component (HCC), comprising 85 by volume of winter A98 gasoline and 15 by volume of gas condensate, and the additive mixture 1, comprising 40 by volume of ethanol and 60 by volume of methylbenzoate.
Figure 2 demonstrates that employment of this additive mixture comprising ethanol and the oxygen-containing additive other than ethanol enables to obtain ethanolcontaining gasolines, the vapour pressure of which does not exceed the vapour pressure of the source hydrocarbon component (HCC).
Similar results for DVPE were obtained for the fuel mixtures of the additive mixture, comprising 40 by volume of ethanol and 60 by volume of methylbenzoate, and hydrocarbon component comprising 15 by volume of gas condensate (GC) and by volume of A92 or A95 winter gasoline.
Similar results were obtained when other oxygen-containing compounds and C 6
-C
1 2 hydrocarbons of this invention were used in the proportion of the invention to formulate the additive mixture, which was then used for preparation of the ethanolcontaining gasolines.
These gasoline mixtures of the invention have a vapour pressure equivalent (DVPE) which does not exceed the DVPE of the source hydrocarbon component (HCC). At the same time it is possible to add the oxygen-containing additive only in the amount sufficient to obtain the ethanol-containing gasoline entirely in compliance with requirements for the motor fuels used in the standard internal combustion spark ignition engines.
EXAMPLE Example 5 demonstrates the possibility of reducing the dry vapour pressure equivalent of the ethanol-containing motor fuel for the cases when the hydrocarbon WO 01/53437 WO 0153437PCT/SEO 1/00040 74 base of the fuel is a reformulated gasoline with dry vapour pressure equivalent according to ASTM D-5191 at a level of 27.5 kPa (about 4 psi).
To prepare the mixtures of this composition lead-free reformulated gasoline purchased in Sweden from Preem and in Russia from Lukoil, and the Petroleum benzine purchased from Merck in Germany were used.
The hydrocarbon component (HCC) for the motor fuel compositions was prepared by mixing about 85 by volume of winter A92, A95 or A98 gasoline with about by volume of gas condensate hydrocarbon liquid (GC).
The source gasolines comprised aliphatic and alicyclic 06-012 hydrocarbons, including saturated and unsaturated.
Fig. 1 demonstrates the behaviour of the DVPE of the ethanol-containing motor fuel based on reformulated gasoline A92 and Petroleum benzine. Similar behaviour was observed for the ethanol-containing motor fuel based on reformulated A95 and A98 gasoline, and Petroleum benzine.
It should be pointed out that addition of ethanol to the reformulated gasoline induces a higher vapour pressure increase compared to the addition of ethanol to the standard gasoline.
Gasoline comprising 80 by volume of reformulated gasoline A92 and 20 by volume of Petroleum benzine (PB) had the following properties: DVPE =27.5 kPa.
Anti-knock index O.5(RON MON)=85.5 The comparative fuel 5-1 contained A92 reformulated gasoline, Petroleum benzine (PB) and ethanol and had the following properties for the various compositions: A92: PB :Ethanol= 76: 19: 5 %by volumne DVPE =36.5 kPa 0.59(RON MON) =89.0 WO 01/53437 WO 0153437PCT/SE01/00040 A92: PB: Ethanol= 72: 18: 10 by volume DVPE =36.0 kPa.
MON) =90.7 The inventive fuel 5-2 contained A92 reformulated gasoline, Petroleum benzine (PB), ethanol and the oxygen-containing additive and had the following properties for the vanious compositions: A92 PB Ethanol: Isoamyl alcohol 64: 16: 10: 10 by volume DVPE 27.0 kPa.
MOMK 90.5 A92*: PB Ethanol: Diisobutyl. ether 64: 16: 10: 10 by volume DVPE =27.5 kPa MON) 90.8 A92 PB Ethanol: n-Butanol =64: 16: 10: 10 by volume DVPE =27.5 kPa.
0.5(RON MON) 90.1 A92 PB :Ethanol: 2,4,4-Trimethyl-l-pentanol 64 16 10: 10 by volume DVPE =25.0 kPa.
0.5(RON MON) =91.8 The fuel 5-3 contained reformulated A92 gasoline, Petroleum benzine ethanol, the oxygen-containing additives and also C 8
-C
12 hydrocarbons and had the following properties for the various compositions: A92 PB Ethanol: Isoamyl. alcohol: Naphtha 60 :15 9.2 0.8 :15 by volume The boiling temperature for the naphtha is 140-200"C.
DVPE =27.5 kPa WO 01/53437 WO 0153437PCT/SE01/00040 76 MON) 89.3 A92 :PB :Ethanol n-Butanol Naphtha: Xylene =60: 15 0.8 by volume The boiling temperature for the naphtha is 140-2000C.
DVPE 27.5 kPa MON) 91.2 A92 PB Ethanol Tetrahydrofurfuryl alcohol Isopropylbenzene =60:15: 9:1:l5 %by volume DVPE 27.5 kPa.
MON) 91.3 The fuel compositions below demonstrate the possibility of adjusting the dry vapour pressure equivalent of the ethanol-containing gasolines based on reformulated A98 gasoline and Petroleumn benzine (PB).
The motor fuel comprising 80 by volume of reformulated gasoline A98 and 20 by volume of Petroleum benzine (PB) had the following properties: DVPE =27.3 kPa Anti-knock index 0.5(RON MON) 88.0 The comparison fuel 5-4 contained A98 reformulated gasoline, Petroleum benzine (PB) and ethanol and had the following properties for the various compositions: A98: PB :Ethanol 76: 19: 5% by volume DVPE 36.3 kPa MON) 91.0 A98 PB Ethanol 72: 18: 10 by volume DVPE 35.8 kPa MON) 92.5 WO 01/53437 WO 0153437PCT/SEOI/00040 77 The fuel 5-5 of the invention contained A98 reformulated gasoline, Petroleum benzine ethanol and the oxygen-containing additives and had the following properties for the various compositions: A98: PB :Ethanol: Isoarnyl. alcohol 64 :16: 10: 10 by volume DVPE 26.9 kPa MON) 92.0 A98 PB Ethanol: n-Amyl alcohol 64 :16: 10: 10 by volume DVPE =26.5 kPa MON) 91.2 A98 PB Ethanol: Linalool. 68 :17 9 6 by volume DVPE= 27.1 kPa 0.5(RON MON) 92.6 A98 PB :Ethanol: 3,6-Ditnethyl-3-octanol 68 :17 9 6 by volume DVPE 27.0 kPa.
MON) =92.5 The fuel 5-6 contained A98 reformulated gasoline, Petroleum benzine ethanol, the oxygen-containing additives, and CS-0 12 hydrocarbons and had the following properties for the various compositions: A98 PB Ethanol: Isoamyl. alcohol Naphtha 60: 15 9.2 0.8: 15 by volume The boiling temperature for the naphtha is 140-200*C.
DVPE 27.0 kPa MON) 91.7 A98 PB: Ethanol: Linalool Allocymene =60: 15: 9: 1: 15 by volume DVPE =26.0 kPa MON) 93.0 WO 01/53437 PCT/SE01/00040 78 A98 PB Ethanol: Methylcyclohexanol: Limonene 60 15 9.5 1 14.5 by volume DVPE 25.4 kPa MON) 93.2 The motor fuel compositions below demonstrate the possibility of adjusting the dry vapour pressure equivalent of the ethanol-containing fuel mixture based on about by volume of reformulated A95 gasoline and about 20 by volume of the Petroleum benzine Gasoline comprising 80 by volume of the reformulated gasoline and 20 by volume of the Petroleum benzine (PB) had the following properties: DVPE 27.6 kPa Anti-knock index 0.5(RON MON) 86.3 The hydrocarbon component (HCC) comprising 80 by volume of reformulated gasoline and 20 by volume of Petroleum benzine (PB) was used as a reference fuel for testing on a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No.
LG4F20-87) in accordance with test method EU 2000 NEDC EC 98/69 and gave the following results: CO 2.631 g/km; HC 0.348 g/km; NOx 0.313 g/km; C02 235.1 g/km; NMHC 0.308 g/km; Fuel consumption, Fc, 1/100km 10.68 The fuel 5-7 contained A95 reformulated gasoline, Petroleum benzine (PB) and ethanol and had the following properties for the various compositions: PB Ethanol 76 19 5 by volume DVPE 36.6 kPa MON) 90.2 WO 01/53437 PCT/SE01/00040 79 PB Ethanol 72 18 10 by volume DVPE 36.1 kPa MON) 91.7 The reference fuel mixture (RFM5) comprising 72 by volume of reformulated gasoline, 18 by volume of Petroleum benzine (PB) and 10 by volume of ethanol was tested on a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No.
LG4F20-87) in accordance with test method EU 2000 NEDC EC 98/69 as above and gave the following results in comparison or with the results for the gasoline comprising 80 by volume of reformulated gasoline A95 and 20 by volume of Petroleum benzine (GC): CO -4.8% HC NOx +26.3%; C02 NMHC Fuel consumption, Fc, 1/100km The fuel 5-8 contained A95 reformulated gasoline, Petroleum benzine ethanol and the oxygen-containing additives and had the following properties for the various compositions: PB Ethanol: Isoamyl alcohol 64 16 10 10 by volume DVPE 27.1 kPa MON) 92.0 PB Ethanol: 2,6-Dimethyl-4-heptanol 64 16 10 10 by volume DVPE 27.0 kPa MON) 92.4 PB Ethanol Tetrahydrofurfuryl acetate 60 15 15 10 by volume DVPE 25.6 kPa WO 01/53437 PCT/SE01/00040 MON) 93.0 The fuel 5-9 contained A95 reformulated gasoline, Petroleum benzine ethanol, the oxygen-containing additives, and C 8
-C
12 hydrocarbons and had the following properties for the various compositions: PB Ethanol: Isoamyl alcohol Naphtha 60 15 9.2 0.8 15 by volume The boiling temperature for the naphtha is 140-200°C.
DVPE 27.1 kPa MON) 91.4 PB Ethanol: Tetrahydrofurfuryl alcohol Tert-butylcyclohexane 60 9.2 0.8 15 by volume DVPE 26.5 kPa MON) 90.7 PB Ethanol: 4-Methyl-4-hydroxytetrahydropyran Isopropyltoluene 15 9.2 0.8 15 by volume DVPE 26.1 kPa MON) 92.0 The motor fuel 5-10 contained 60% by volume of A95 reformulated gasoline, by volume of Petroleum benzine 10% by volume of ethanol, 5% by volume of 2,5-Dimethyltetrahydrofuran and 10% by volume of isopropyltoluene. Formulation 5-10 was tested to demonstrate how the invention enables the formulation of ethanol-containing gasoline with a low vapour pressure, wherein the presence in the motor fuel composition of ethanol does not induce an increase of dry vapour pressure equivalent in comparison to the source hydrocarbon component (HCC). Moreover, this gasoline secures a decrease of toxic emissions in the exhaust and a decrease of the fuel consumption in comparison with the above mixture RFM 5. The formulation 5-10 had the following specific properties: density at 15°C, according to ASTM WO 01/53437 PCT/SE01/00040 D4052 initial boiling point, according to ASTM D 86 vaporisable portion 70C vaporisable portion 100°C vaporisable portion 150°C vaporisable portion 190C final boiling point evaporation residue loss by evaporation oxygen content, according to ASTM D4815 acidity, according to ASTM D1613 weight% HAc pH, according to ASTM D1287 sulfur content, according to ASTM D 5453 gum content, according to ASTM D381 water content, according to ASTM D6304 aromatics, according to SS 155120, including benzene benzene alone, according to EN 238 DVPE, according to ASTM D 5191 anti-knock index 0.5(RON+MON), according to ASTM D 2699-86 and ASTM D 2700-86 764.6 kg /m3; 48.9"C; 25.3 by volume; 50.8 by volume; 76.5 by volume; 95.6 by volume; 204.5"C; 1.4 by volume; 0.5 by volume; 4.6% w/w; 0.08; 39 mg/kg; 1.5 mg/100ml; 0.1% w/w; 38 by volume; 0.4 by volume; 27.2 kPa; 91.8 The motor fuel Formulation 5-10 was tested as described previously and gave the following results in comparison or with the results for the motor fuel comprising 80 by volume of reformulated A95 gasoline and 20 by volume of Petroleum benzine:
CO
HC
NOx CO2
NMHC
-12.3% unchanged; WO 01/53437 PCT/SEO 1/00040 82 Fuel consumption, Fc, 1/100km +3.7% Similar results are obtained when other oxygen-containing additives of the invention substitute the oxygen-containing additives of the examples 5-1 to 5-10.
To prepare all the above fuel formulations 5-1 to 5-10 of this motor fuel composition, initially the hydrocarbon component (HCC) which is a mixture of reformulated gasoline and Petroleum benzine (PB) was mixed with ethanol, to which mixture then was added the corresponding oxygen-containing additive and Cs-C 12 hydrocarbons.
The motor fuel composition obtained was then allowed to stand before testing between 1 and 24 hours at a temperature not lower than -35"C. All the above formulations were prepared without the use of any mixing devices.
The invention demonstrated the possibility of adjusting the vapour pressure of the ethanol-containing motor fuels for the standard internal combustion spark ignition engines based on non-standard gasolines having a low vapour pressure.
Figure 2 shows the behaviour of the dry vapour pressure equivalent (DVPE) when mixing the hydrocarbon component (HCC), comprising 80 by volume of reformulated A92 gasoline and 20 by volume of Petroleum benzine, with the oxygencontaining additive mixture 5, comprising 40 by volume of ethanol, 20 by volume of 3,3,5-trimethylcyclohexanone, and 20 by volume of naphtha with boiling temperature 130-170°C and 20 by volume of tert-butyltoluene. The graph demonstrates that the use of the additive of this invention enables obtaining ethanolcontaining gasolines, the vapour pressure of which does not exceed the vapour pressure of the source hydrocarbon component (HCC).
Similar DVPE behaviour was demonstrated when mixing the above oxygencontaining additive with hydrocarbon component (HCC) comprising 20 by volume of Petroleum benzine (GC) and 80 by volume of A95 or A98 reformulated gasoline.
Similar results were obtained when other oxygen-containing compounds and C8-C12 hydrocarbons of this invention were used in the proportion of the invention to for- WO 01/53437 PCT/SEO1/00040 83 mulate the oxygen-containing additive, which was then used for preparation of the ethanol-containing gasolines.
These gasolines have a vapour pressure equivalent (DVPE) not higher than the DVPE of the source hydrocarbon component (HCC). At the same time the antiknock index for all ethanol-containing gasolines prepared in accordance with this invention was higher than that of the source hydrocarbon component (HCC).
The foregoing description and examples of preferred embodiments of this invention should be taken as illustrating, rather than as limiting, the present invention as defined by the claims. As will be readily appreciated, numerous variations and combinations of the features set forth above can be used without departing from the present invention as set forth in the claims. All such modifications are intended to be included within the scope of the following claims.

Claims (20)

1. A method of reducing the vapour pressure of a C 3 -C 1 2 hydrocarbon-based motor fuel mixture for conventional spark ignition internal combustion engines containing 0.1 to 20% by volume of ethanol, not more than 0.25% by weight of water according to ASTM D 6304, and not more than 7% by weight of oxygen according to ASTM D 4815, wherein, in addition to a C 3 -C 1 2 hydrocarbon component and an ethanol component an oxygen-containing component is present in the fuel mixture in an amount from 0.05 to 15% by volume of the total volume of the fuel mixture; the component being selected from at least one of the following types of compounds: alkanol, having from 3 to 10 carbon atoms; dialkyl ether, having from 6 to 10 carbon atoms; ketone, having from 4 to 9 carbon atoms; alkyl ester of alkanoic acid, having from 5 to 8 carbon atoms; hydroxyketone, having from 4 to 6 carbon atoms; ketone ester of alkanoic acid, having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl-
4-oxytetrahydropyran, and the mixtures thereof; and a component selected from at least one C 6 -C 2 hydrocarbon, is present in the fuel mixture in an amount such that the ratio is from 1:200 to 200:1 by volume. 2. The method of claim 1, wherein the oxygen-containing component and component are added to the ethanol component which mixture of(c), and (d) is subsequently added to the hydrocarbon component 3. The method of claim 1, wherein the ethanol component is added to the hydrocarbon component to which mixture of and the oxygen-containing component and component are added. 4. The method of any one of claims 1 to 3, wherein the C 3 -Ci 2 hydrocarbon 30 component is selected from the group consisting of a non-reformulated standard type gasoline, a hydrocarbon liquid from petroleum refining, a hydrocarbon liquid from natural gas, a hydrocarbon liquid from an off-gas of chemical-recovery carbonisation, a hydrocarbon liquid from synthesis gas processing, or mixtures thereof. [R:ALIBZZ]041 34.doc:aak The method of claim 4 wherein the C 3 -CI 2 hydrocarbon component is a non- reformulated standard type gasoline.
6. The method of any one of claims 1 to 5, wherein the fuel composition obtained exhibits the following characteristics: a density at 15 0 C, according to ASTM D 4052 of at least 690 kg/m 3 (ii) a dry vapour pressure equivalent according to ASTM D 5191 from kPa to 120 kPa; (iii) an acids content according to ASTM D 1613 of no greater than 0.1 weight HAc; (iv) a pH according to ASTM D 1287 from 5 to 9; an aromatics content according to SS 155120 of no greater than 40% by volume, wherein benzene is present in amounts according to EN 238 no greater than 1% by volume; (vi) a sulphur content according to ASTM D 5453 of no greater than mg/kg; (vii) a gum content according to ASTM D 381 of no greater than 2 mg/100 ml; (viii) distillation properties according to ASTM D86 wherein initial boiling point is at least 20 0 C; a vaporisable portion at 70 0 C is at least 25% by volume; a vaporisable portion at 100 0 C is at least 50% by volume; a vaporisable portion at 150 0 C is 99 at least 75% by volume; a vaporisable portion at 190 0 C is at least 95% by volume; a final boiling point no greater than 205 0 C; and an evaporation residue no greater than 2% by volume; and (ix) an anti-knock index 0.5 (RON+MON) according to ASTM D 2699-86 and ASTM D 2700-86 of at least
7. A C 3 -C 1 2 hydrocarbon-based motor fuel composition for a conventional internal combustion spark ignition engine, containing from 0.1 to 20% by volume of ethanol, not more than 0.25% by weight of water according to ASTM D6304, and not more than 7% by weight of oxygen according to ASTM D4815, having a reduced vapour 30 pressure, comprising: a C 3 -C 1 2 hydrocarbon component; .9 a fuel grade ethanol in an amount of 0.1-20% by volume of the total volume of the motor fuel composition; an oxygen-containing component comprising at least one of the following types of compounds: [R:\LIBZZ]041 34.doc:aak 86 alkanol having from 3 to 10 carbon atoms; dialkyl ether having from 6 to 10 carbon atoms; ketone having from 4 to 9 carbon atoms; alkyl ester ofalkanoic acid having from 5 to 8 carbon atoms; hydroxyketone having from 4 to 6 carbon atoms; ketone ester ofalkanoic acid having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl- 4-oxytetrahydropyran, and mixtures thereof, said oxygen-containing component being present in an amount of 0.05 to 15% by volume of the total volume of the motor fuel composition; at least one C 6 -C 1 2 hydrocarbon, preferably Cs-CIn hydrocarbon, present in an amount such that the ratio is from 1:200 to 200:1 by volume.
8. The composition of claim 7 wherein the fuel grade ethanol is present in an amount of 1 to 20% by volume of the total volume of the motor fuel composition.
9. The composition of claim 7 wherein the fuel grade ethanol is present in an amount of 3 to 15 by volume of the total volume of the motor fuel composition. The composition of claim 7 wherein the fuel grade ethanol is present in an 0 •20 amount of 5 to 10% by volume of the total volume of the motor fuel composition.
11. The composition of any one of claims 7 to 10 wherein the oxygen-containing component is present in an amount of 0.1 to 15% by volume of the total volume of the motor fuel composition.
12. The composition of any one of claims 7 to 10 wherein the oxygen-containing component is present in an amount of 3 to 10% by volume of the total volume of the motor fuel composition.
13. The composition of any one of claims 7 to 10 wherein the oxygen-containing component is present in an amount of 5 to 10% by volume of the total volume of the motor fuel composition.
14. A mixture of a fuel grade ethanol an oxygen-containing component and at least one C 6 -CI 2 hydrocarbon which can be used in the method of claim 1, wherein: [R:\LIBZZ]041 34.doc:aak 87 the ethanol component is present in an amount of 0.5 to 99.5%, by volume of the total volume of the mixture; the oxygen-containing component is selected from at least one of the following types of compounds: alkanol having from 3 to 10 carbon atoms; dialkyl ether having from 6 to 10 carbon atoms; ketone having from 4 to 9 carbon atoms; alkyl ester of alkanoic acid having from 5 to 8 carbon atoms; hydroxyketone having from 4 to 6 carbon atoms; ketone ester of alkanoic acid having from 5 to 8 carbon atoms; oxygen-containing heterocyclic compound selected from the following: tetrahydrofurfuryl alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran, tetramethyltetrahydrofuran, methyl tetrahydropyran, 4-methyl- 4-oxytetrahydropyran, and mixtures thereof, and is present in an amount of 0.5 to 99.5%, by volume of the total volume of the mixture; component comprising at least one C 6 -C 2 hydrocarbon, preferably C 8 -C I hydrocarbon, in an amount present in an amount such that the ratio is from 1:200 to 200:1 by volume. The mixture of claim 14 wherein the ethanol component is present in an amount of 9.5 to 99% by volume of the total volume of the mixture.
16. The mixture of claim 14 wherein the ethanol component is present in an Samount of 20 to 95% by volume of the total volume of the mixture.
17. The mixture of claim 14 wherein the ethanol component is present in an amount of 25 to 92% by volume of the total volume of the mixture.
18. The mixture of any one of claims 14 to 17 wherein the oxygen containing component is present in an amount of 0.5 to 90% by volume of the total volume of the mixture.
19. The mixture of any one of claims 14 to 17 wherein the oxygen containing component is present in an amount of 0.5 to 80% by volume of the total volume of the mixture.
20. The mixture of any one of claims 14 to 17 wherein the oxygen containing component is present in an amount of 3 to 70% by volume of the total volume of the mixture.
21. The mixture of any one of claims 14 to 20, wherein the fuel grade ethanol comprises at least 99.5% by volume of ethanol. [R:\LIBZZ]41 34.doc:aak 88
22. The mixture of any one of claims 14 to 20, wherein the component is a denatured ethanol mixture as it is supplied to the market, comprising about 92% by volume of ethanol and the remaining to 100% part of the component is hydrocarbons and by-products. s 23. The mixture of any one of claims 14 to 22, wherein the component is an individual aliphatic saturated and unsaturated, or alicyclic saturated or unsaturated hydrocarbon, or mixtures thereof, and/or hydrocarbon fraction boiling at 100-200 0 C, obtained in distillation of oil, bituminous coal resin or products yielded from processing of synthesis-gas.
24. Use of the mixture of any one of claims 14 to 23 as a motor fuel in a modified internal combustion spark ignition engine. Use of the mixture of any one of claims 14 to 23 for obtaining a gasoline fuel, containing components for conventional internal combustion spark ignition engines and adjusting the octane number of such a fuel to a desired level by mixing a corresponding amount of said mixture with a conventional gasoline fuel while maintaining or decreasing the vapour pressure of the thus-obtained fuel composition as compared to the level of the vapour pressure of the gasoline component alone.
26. Use of the composition of any one of claims 7 to 13 for reducing the fuel consumption as compared to corresponding gasoline-ethanol mixture comprising 4components 4O*4 4...i
427. Use of the composition of any one claims 7 to 13 for reducing the content of harmful substances in the exhaust emissions as compared to corresponding gasoline- ethanol mixture comprising components 28. Use of claim 26 or claim 27, wherein the content of oxygen in the motor fuel is not more than 7% by weight, of the total weight of the fuel. 29. The use of claim 26 or claim 27 wherein the content of oxygen in the motor V, fuel is not more than 5% by weight, of the total weight of the fuel. A method of reducing the vapour pressure of a C 3 -C 1 2 hydrocarbon-based S 30 motor fuel mixture for conventional spark ignition internal combustion engines oo, 'substantially as hereinbefore described with reference to any one of the examples, but excluding the comparative examples. o o [R:\LIBZZ]04 34.doc:aak 89 31. A C 3 -CI 2 hydrocarbon-based motor fuel composition for a conventional internal combustion spark ignition engine, substantially as hereinbefore described with reference to any one of the examples, bui excluding the comparative examples. 32. A mixture of fuel grade ethanol, an oxygen-containing component, and at least one C 6 -CI 2 hydrocarbon substantially as hereinbefore described with reference to any one of the examples, but excluding the comparative examples. Dated 9 April, 2003 Angelica Hull Patent Attorneys for the Applicant/Nominated Person 1o SPRUSON FERGUSON oo:** 0* 0 a OdG* S 565 S.. S~ S S 0 [R\LIBZZj04134.doc:aak
AU28949/01A 2000-01-24 2001-01-24 Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines Ceased AU782062B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AU36848/00 2000-01-24
PCT/SE2000/000139 WO2001053436A1 (en) 2000-01-24 2000-01-24 Motor fuel for spark ignition internal combustion engines
PCT/SE2001/000040 WO2001053437A1 (en) 2000-01-24 2001-01-24 Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines

Publications (2)

Publication Number Publication Date
AU2894901A AU2894901A (en) 2001-07-31
AU782062B2 true AU782062B2 (en) 2005-06-30

Family

ID=20278139

Family Applications (2)

Application Number Title Priority Date Filing Date
AU36848/00A Abandoned AU3684800A (en) 2000-01-24 2000-01-24 Motor fuel for spark ignition internal combustion engines
AU28949/01A Ceased AU782062B2 (en) 2000-01-24 2001-01-24 Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines

Family Applications Before (1)

Application Number Title Priority Date Filing Date
AU36848/00A Abandoned AU3684800A (en) 2000-01-24 2000-01-24 Motor fuel for spark ignition internal combustion engines

Country Status (30)

Country Link
EP (2) EP1252268B1 (en)
JP (1) JP4871475B2 (en)
KR (1) KR100545054B1 (en)
CN (1) CN1177914C (en)
AT (1) ATE296342T1 (en)
AU (2) AU3684800A (en)
BG (1) BG66039B1 (en)
BR (1) BR0107817B1 (en)
CA (1) CA2397579C (en)
CU (1) CU23146A3 (en)
CZ (1) CZ305710B6 (en)
DE (1) DE60111018T2 (en)
DK (1) DK1252268T3 (en)
EA (1) EA006855B1 (en)
EE (1) EE05647B1 (en)
ES (1) ES2243510T3 (en)
HK (1) HK1052023A1 (en)
HR (1) HRP20020670B1 (en)
HU (1) HU230551B1 (en)
IL (1) IL150624A (en)
MX (1) MXPA02007148A (en)
NO (1) NO336184B1 (en)
PL (1) PL194561B1 (en)
PT (1) PT1252268E (en)
RS (1) RS52075B (en)
SI (1) SI1252268T1 (en)
SK (1) SK287660B6 (en)
UA (1) UA76945C2 (en)
WO (2) WO2001053436A1 (en)
ZA (1) ZA200205833B (en)

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6761745B2 (en) 2000-01-24 2004-07-13 Angelica Hull Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
US7981170B1 (en) * 2000-04-21 2011-07-19 Shell Oil Company Gasoline-oxygenate blend and method of producing the same
US6565617B2 (en) * 2000-08-24 2003-05-20 Shell Oil Company Gasoline composition
WO2003062354A1 (en) * 2002-01-21 2003-07-31 Ramar Ponniah Hydrocarbon fuel
JP2005187706A (en) * 2003-12-26 2005-07-14 Japan Energy Corp Ethanol-containing gasoline and method for manufacturing the same
AU2011226816B2 (en) * 2005-01-25 2012-08-30 Bp Corporation North America Inc. Reduced RVP oxygenated gasoline composition and method
NZ590060A (en) * 2005-01-25 2012-12-21 Bp Corp North America Inc Reduced rvp oxygenated gasoline composition and method
US20090199464A1 (en) * 2008-02-12 2009-08-13 Bp Corporation North America Inc. Reduced RVP Oxygenated Gasoline Composition And Method
JP4624143B2 (en) * 2005-03-11 2011-02-02 コスモ石油株式会社 Ethanol blended gasoline
JP4624142B2 (en) * 2005-03-11 2011-02-02 コスモ石油株式会社 Ethanol blended gasoline
US7389751B2 (en) * 2006-03-17 2008-06-24 Ford Global Technology, Llc Control for knock suppression fluid separator in a motor vehicle
EP2038530A4 (en) 2006-05-26 2011-04-27 Amyris Biotechnologies Inc Fuel components, fuel compositions and methods of making and using same
MY146612A (en) 2006-05-26 2012-09-14 Amyris Inc Production of isoprenoids
KR100812423B1 (en) * 2006-12-13 2008-03-10 현대자동차주식회사 Method for calculating concentration of ethanol in fuel and apparatus for the same
WO2008088212A1 (en) 2007-01-15 2008-07-24 Technische Universiteit Eindhoven A liquid fuel composition and the use thereof
NL1033228C2 (en) * 2007-01-15 2008-07-16 Univ Eindhoven Tech Liquid fuel composition useful in compression-ignition engine, comprises a mixture of hydrocarbons containing a cyclic hydrocarbon compound having at least five carbon atoms and at least one oxygen atom
DE102008008818A1 (en) * 2008-02-12 2009-08-20 Deutsche Bp Ag Fuels for petrol engines
EP2265698A4 (en) * 2008-03-12 2012-03-07 Ramar Ponnupillai Velar bio hydrocarbon fuel
US9476004B2 (en) 2009-09-08 2016-10-25 Technische Universiteit Eindhoven Liquid fuel composition and the use thereof
JP5144729B2 (en) * 2010-09-10 2013-02-13 コスモ石油株式会社 Production method of ethanol blended gasoline
JP5214688B2 (en) * 2010-09-10 2013-06-19 コスモ石油株式会社 Production method of ethanol blended gasoline
WO2012120147A1 (en) 2011-03-10 2012-09-13 Shell Internationale Research Maatschappij B.V. Improvements relating to gasoline fuel formulations
EP2722383B1 (en) * 2011-08-17 2018-05-23 Hunan Zhongchuang Chemical Co., Ltd A gasoline composition and its preparation method
NL2007304C2 (en) * 2011-08-26 2013-02-27 Progression Industry B V Use of perfume composition as fuel for internal combustion engines.
US8968429B2 (en) * 2011-09-23 2015-03-03 Butamax Advanced Biofuels Llc Butanol compositions for fuel blending and methods for the production thereof
CN102746909B (en) * 2012-07-20 2014-04-16 杨如平 Methanol fuel modifier and high-proportion methanol fuel for gasoline engine
CN102876404B (en) * 2012-10-11 2014-10-22 陕西延长石油(集团)有限责任公司研究院 Additive capable of reducing methanol gasoline saturated vapor pressure
ITMI20122006A1 (en) * 2012-11-26 2014-05-27 Eni Spa USEFUL COMPOSITIONS AS FUELS INCLUDING HYDROPHOBIC OXYGENATED COMPOUNDS
CN104004554B (en) * 2014-06-05 2016-01-20 上海化工研究院 Vehicle alcohol-ether substitute fuel tail gas activator and its preparation method and application
BR112017005960B1 (en) * 2014-10-06 2021-08-24 Shell Internationale Research Maatschappij B.V. USE OF A LIQUID HYDROCARBIDE COMPOSITION
US11913166B2 (en) 2015-09-21 2024-02-27 Modern Meadow, Inc. Fiber reinforced tissue composites
RU2605952C1 (en) * 2015-12-25 2017-01-10 Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") Alternative motor fuel and production method thereof
RU2605954C1 (en) * 2015-12-25 2017-01-10 Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") Alternative motor fuel and production method thereof
ES2767369T3 (en) 2015-12-29 2020-06-17 Neste Oyj Method of producing a fuel mixture
EP3205702A1 (en) 2016-02-11 2017-08-16 Bp Oil International Limited Fuel compositions with additives
EP3205701A1 (en) 2016-02-11 2017-08-16 Bp Oil International Limited Fuel compositions
EP3205703A1 (en) 2016-02-11 2017-08-16 Bp Oil International Limited Fuel additives
US11542374B2 (en) 2016-02-15 2023-01-03 Modern Meadow, Inc. Composite biofabricated material
RU2616606C1 (en) * 2016-04-14 2017-04-18 Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") High-octane motor gasoline and anti-knock additive for production thereof
ES2862192T3 (en) 2016-09-29 2021-10-07 Neste Oyj Diesel fuel comprising 5-nonanone
EP3399008B1 (en) 2017-05-02 2020-03-18 ASG Analytik-Service Gesellschaft mbH Potentially co2-neutral and ecological gasoline based on c1-chemistry
AU2018253595A1 (en) 2017-11-13 2019-05-30 Modern Meadow, Inc. Biofabricated leather articles having zonal properties
MX2021008462A (en) 2019-01-17 2021-08-19 Modern Meadow Inc Layered collagen materials and methods of making the same.
RU2740554C1 (en) * 2020-08-13 2021-01-15 федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" High-octane gasoline
FI20205840A (en) * 2020-08-31 2022-03-01 Neste Oyj Octane enhanced intermediate hydrocarbon composition
FI129568B (en) 2021-04-15 2022-04-29 Neste Oyj 2-butanone and ethanol as gasoline components
WO2023089354A1 (en) * 2021-11-16 2023-05-25 Hediger Richard Method for producing a fuel additive

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328004A (en) * 1980-08-13 1982-05-04 United International Research, Inc. Stabilization of ethanol-gasoline mixtures
US4541836A (en) * 1982-12-09 1985-09-17 Union Carbide Corporation Fuel compositions

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2104021A (en) * 1935-04-24 1938-01-04 Callis Conral Cleo Fuel
US2365009A (en) * 1940-12-19 1944-12-12 Standard Oil Dev Co Motor fuels
RO75851A2 (en) * 1978-02-22 1981-02-28 Institutul National De Motoare Termice,Ro COMBUSTIBLE MIXTURE
US4207076A (en) * 1979-02-23 1980-06-10 Texaco Inc. Gasoline-ethanol fuel mixture solubilized with ethyl-t-butyl ether
DK148747C (en) * 1980-06-09 1986-02-24 Inst Francais Du Petrole motor fuel
FR2493863A1 (en) * 1980-11-07 1982-05-14 Inst Francais Du Petrole NEW FUEL BASED ON FUEL CONTAINING ETHANOL HYDRATE AND AN ADDITIVE
DE3150989A1 (en) * 1980-12-30 1982-08-05 Institut Français du Pétrole, 92502 Rueil-Malmaison, Hauts-de-Seine COMBUSTIBLE COMPOSITIONS CONTAINING A GAS OIL, AT LEAST ONE FATTY ACID ESTER AND AN ALCOHOLIC COMPONENT BASED ON N-BUTANOL, AND ARE USED AS DIESEL FUELS
FR2500844A1 (en) * 1981-03-02 1982-09-03 Realisations Sarl Et Preventing phase-sepn. of mixt. of hydrocarbon fuel and an alcohol - using additive mixt. contg. benzyl alcohol and acetate
DE3116734C2 (en) * 1981-04-28 1985-07-25 Veba Oel AG, 4650 Gelsenkirchen Carburetor fuel
US4451266A (en) * 1982-01-22 1984-05-29 John D. Barclay Additive for improving performance of liquid hydrocarbon fuels
DE3478465D1 (en) * 1983-03-03 1989-07-06 Union Rheinische Braunkohlen Motor fuel
DE3330165C2 (en) * 1983-08-20 1985-10-03 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln Engine fuel
US4891050A (en) * 1985-11-08 1990-01-02 Fuel Tech, Inc. Gasoline additives and gasoline containing soluble platinum group metal compounds and use in internal combustion engines
US4806129A (en) * 1987-09-21 1989-02-21 Prepolene Industries, Inc. Fuel extender
US4818250A (en) * 1987-10-21 1989-04-04 Lemco Energy, Inc. Process for producing fuel from plant sources and fuel blends containing same
ES2012729A6 (en) * 1989-06-07 1990-04-01 Vicente Rodriguez Heliodoro Oxygenated organic fuel additive prepn. - by making seven mixts., emulsifying and standing, followed by combining, homogenising and standing
CN1017061B (en) * 1990-02-13 1992-06-17 唐昌干 Anti-knocking, fume-reducing, oil-saving agent for vehicles and ships and process for producing same
DE4308053C2 (en) * 1993-03-13 1997-05-15 Veba Oel Ag Liquid unleaded fuels
US5607486A (en) * 1994-05-04 1997-03-04 Wilkins, Jr.; Joe S. Engine fuels
US5688295A (en) * 1996-05-08 1997-11-18 H. E. W. D. Enterprises-America, Inc. Gasoline fuel additive
US5697987A (en) * 1996-05-10 1997-12-16 The Trustees Of Princeton University Alternative fuel
CA2317399C (en) * 1998-01-12 2009-01-27 Deborah Wenzel An additive composition also used as a fuel composition comprising water soluble alcohols

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4328004A (en) * 1980-08-13 1982-05-04 United International Research, Inc. Stabilization of ethanol-gasoline mixtures
US4541836A (en) * 1982-12-09 1985-09-17 Union Carbide Corporation Fuel compositions

Also Published As

Publication number Publication date
ES2243510T3 (en) 2005-12-01
PL194561B1 (en) 2007-06-29
EA006855B1 (en) 2006-04-28
EP1252268A1 (en) 2002-10-30
DE60111018T2 (en) 2006-01-26
CZ305710B6 (en) 2016-02-17
BG66039B1 (en) 2010-11-30
HRP20020670A2 (en) 2004-12-31
HU230551B1 (en) 2016-11-28
PT1252268E (en) 2005-09-30
EE200200407A (en) 2003-12-15
CU23146A3 (en) 2006-06-29
JP4871475B2 (en) 2012-02-08
UA76945C2 (en) 2006-10-16
EP1252268B1 (en) 2005-05-25
SK287660B6 (en) 2011-05-06
RS52075B (en) 2012-06-30
ATE296342T1 (en) 2005-06-15
CZ20022869A3 (en) 2003-04-16
BR0107817B1 (en) 2010-11-30
IL150624A0 (en) 2003-02-12
PL356843A1 (en) 2004-07-12
AU2894901A (en) 2001-07-31
BR0107817A (en) 2002-11-05
CN1395611A (en) 2003-02-05
WO2001053436A1 (en) 2001-07-26
SI1252268T1 (en) 2005-10-31
JP2003520891A (en) 2003-07-08
DE60111018D1 (en) 2005-06-30
EA200200796A1 (en) 2002-12-26
CA2397579A1 (en) 2001-07-26
BG107007A (en) 2003-11-28
CA2397579C (en) 2010-02-16
NO20023502L (en) 2002-09-24
YU55802A (en) 2005-03-15
DK1252268T3 (en) 2005-09-12
WO2001053437A1 (en) 2001-07-26
MXPA02007148A (en) 2005-07-01
CN1177914C (en) 2004-12-01
EE05647B1 (en) 2013-04-15
AU3684800A (en) 2001-07-31
EP1589091A1 (en) 2005-10-26
ZA200205833B (en) 2003-10-01
HUP0204201A2 (en) 2003-05-28
KR20020082214A (en) 2002-10-30
HRP20020670B1 (en) 2010-05-31
WO2001053437A8 (en) 2001-12-20
NO336184B1 (en) 2015-06-08
NO20023502D0 (en) 2002-07-23
SK12222002A3 (en) 2003-08-05
HK1052023A1 (en) 2003-08-29
KR100545054B1 (en) 2006-01-24
IL150624A (en) 2005-06-19

Similar Documents

Publication Publication Date Title
AU782062B2 (en) Method of reducing the vapour pressure of ethanol-containing motor fuels for spark ignition combustion engines
US6761745B2 (en) Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
PL192476B1 (en) Fuel compositions
US20010034966A1 (en) Method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines
JP2004244532A (en) Gasoline
JP2004285204A (en) Gasoline
JP2004285205A (en) Gasoline
JP4691269B2 (en) Fuel oil composition for gasoline engines
JP4237287B2 (en) Unleaded gasoline composition
JP4920185B2 (en) Gasoline composition
CN102127467A (en) Ether fuel
JP2005187519A (en) Ethanol-containing gasoline
JP4746868B2 (en) gasoline
JP4746869B2 (en) High performance gasoline
JPH06192667A (en) Gasoline composition
WO2010000759A1 (en) Gasoline compositions
JP2006160922A (en) Gasoline composition
JP2006160917A (en) Gasoline composition

Legal Events

Date Code Title Description
MK14 Patent ceased section 143(a) (annual fees not paid) or expired