Note: Descriptions are shown in the official language in which they were submitted.
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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 ad-
justing 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
ex-
tensive 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
bal-
ance 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 burn
more
cleanly.
The existing global inventory of vehicles and machinery operating with spark
igni-
tion internal combustion engines does not allow currently the complete
elimination
of gasoline as a motor fuel.
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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 re-
sources for yielding motor fuel components.
U.S. Patent No. 2,365,009, issued in 1944 describes the combination of Ci_5,
alco-
hols and C3_5 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 refming,
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
com-
parison to the combustion of gasoline. However, the use of a motor fuel
principally
containing ethanol requires specially designed engines. At the same time spark
ig-
nition 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.
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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 C.The gasolines known as A92 and
A95 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 al-
lowed 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 - Cio intermediate gasoline. Such fuels are said to
better
facilitate the addition of alcohol over current gasoline because of their
lower dry va-
pour 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 gas-
olines 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 com-
pounds comprising, in addition to gasoline, ketones, nitro-paraffin and also
alco-
hols other than ethanol. It is noted that the composition of the catalytic
clean-
combustion-promoter disclosed in the patent reduces the DVPE of gasoline fuel.
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Nothing is mentioned in this patent about the impact of the clean-combustion-
promoter 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 com-
pound as an additive to gasoline or as a fuel for standard gasoline engines.
In ac-
cordance 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 -
45% 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
com-
bustion, 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
de-
scribed. A spark ignition motor fuel composition is also disclosed, including
a hy-
drocarbon component of C5 - C8 straight-chained or branched alkanes,
essentially
free of olefms, aromatics, benzene and sulphur, in which the hydrocarbon compo-
nent 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 compo-
nents 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
het-
erocyclical 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:
(1) It is necessary to use only hydrocarbon components C5 - C8 which are
straight-
chained or branched alkanes (i) free of such unsaturated compounds as olefins,
benzene and other aromatics, (ii) free of sulphur and, as follows from the
descrip-
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tion of the invention, (iii) the hydrocarbon component is a coal gas
condensate or
natural gas condensate;
(2) It is necessary to use as a co-solvent for the hydrocarbon component and
etha-
5 nol only one particular class of chemical compounds containing oxygen;
namely,
ethers, including short-chained and heterocyclic ethers;
(3) It is necessary to use a large quantity of ethanol in the fuel, not less
than 25%;
(4) It is necessary to use a large quantity of co-solvent, not less than 20%,
of 2-
methyltetrahydrofuran; and
(5) It is required to modify the spark ignition internal combustion engine
when op-
erating 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 C3
to C12 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
C3 to
C12 hydrocarbon itself, or at least so as to meet the standard requirement on
gaso-
line fuel.
SUMMARY OF THE INVENTION
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-
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.
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The present inventors have found that specific types of compounds exhibiting
an
oxygen-containing group surprisingly lower the vapour pressure of a gasoline-
ethanol mixture.
This effect can unexpectedly be further enhanced by means of specific C6 - C12
hy-
drocarbon 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
oxygen-
component of the present invention.
According to the present method up to about 20 % by volume of fuel grade
ethanol
(b) can be used in the whole fuel compositions. The oxygen-containing
additives (c)
used can be obtained from renewable raw materials, and the hydrocarbon compo-
nent (a) 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
(b) and
oxygen-containing additive (c), and optionally, the further component (d),
being in-
dividual hydrocarbons of the C6-C12 fraction or their mixtures, which additive
mix-
ture subsequently can be used in the inventive method, i.e., added to the
hydrocar-
bon component (a). The mixture of (b) and (c), and optionally (d), can also be
used
per se as a fuel for modified engines, i.e., not standard-type gasoline
engines. The
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additive mixture can also be used for adjusting the octane number and/or for
low-
ering 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
func-
tion 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 C3 - C12 hydrocarbon fractions as
hydrocar-
bon component (a), 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 - C12 fractions are usually prepared by fractional
distillation or
by blending various hydrocarbons.
Importantly, and as previously mentioned, the component (a) 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.
Ac-
cording to a preferred embodiment the vapour pressure of the hydrocarbon based
ethanol-containing fuel rnixture is reduced by 50% of the ethanol-induced
vapour
pressure increase, more preferably by 80%, and even more preferably the vapour
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8
pressure of the hydrocarbon based ethanol-containing fuel mixture is reduced
to a
vapour pressure corresponding to that of the hydrocarbon component alone,
andJor
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
oxygen-
containing organic compound (c) other than ethanol. The oxygen-containing
organic
compound enables adjustment of (i) 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 sub-
stances in the engine exhaust emissions. The oxygen-containing compound (c)
has
oxygen bound in at least any one of the following functional groups:
0 0
I II I I II I
-C-O-H -C- -C-O-C- -C-O-C-
1 I I I
O H H O H 0
II I II I II 1
-C-C-C- -C-C-C-O-C-
I I {
H 0- H H
~~-C H ~C'
IC C~
\ --C-O-H I I _
CC I iC`O'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 oxygen-
containing rings.
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The fuel additive can be derived from fossil-based sources or preferably from
renew-
able sources such as biomass.
The oxygen-containing fuel additive (c) can typically be an alcohol, other
than etha-
nol. 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, n-
pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, diethylcarbinol,
diiso-
propylcarbinol, 2-ethylhexanol, 2,4,4-trimethylpentanol, 2,6-dimethyl-4-
heptanol,
linalool, 3,6-dimethyl-3-octanol, phenol, phenylmethanol, methylphenol,
methylcy-
clohexanol or similar alcohols, are employed, as well as their mixtures.
The component (c) can also be an aliphatic or alicyclic ketone, both saturated
and
0
11
unsaturated, of the general formula R - C - R' , where R and R' are the same
or
different and are each C1-C6 hydrocarbons, which also can be cyclic, and are
pref-
erably C1-Ca. hydrocarbons. Preferred ketones have a total (R+R') of 4 to 9
carbon
atoms and include methylethyl ketone, methylpropyl ketone, diethylketone, meth-
ylisobutyl ketone, 3-heptanone, 2-octanone, diisobutyl ketone, cyclohexanon,
ace-
tofenone, trimethylcycohexanone, or similar ketones, and mixtures thereof.
The component (c) can also be an aliphatic or alicyclic ether, including both
satu-
rated and unsaturated ethers, of the general formula R-O-R', wherein R and R'
are
the same or different and are each a C1-Cio hydrocarbon group. In general,
lower
(C1-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,
methyli-
soamyl ether, ethylisobutyl ether, ethyltertbutyl ether, dibutyl ether,
diisobutyl
ether, diisoamyl ether, anisole, methylanisole, phenetole or similar ethers
and
mixtures thereof.
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The component (c) may further be an aliphatic or alicyclic ester, including
saturated
0
11
and unsaturated esters, of the general formula R - C - O- R' , where R and R'
are the same or different. R and R' are preferably hydrocarbon groups, more
pref-
erably alkyl groups and most preferably alkyl and phenyl having 1 to 6 carbon
at-
5 oms. Especially preferred is an ester where R is C1-C4 and R' is C4-C6.
Typical esters
are alkyl esters of alkanoic acids, including n-butylacetate, isobutylacetate,
tert-
butylacetate, isobutylpropionate, isobutylisobutyrate, n-amylacetate,
isoamylace-
tate, isoamylpropionate, methylbenzoate, phenylacetate, cyclohexylacetate, or
similar esters and mixtures thereof. In general, it is preferred to employ an
ester
10 having from 5 to 8 carbon atoms.
The additive (c) can simultaneously contain two oxygen-containing groups con-
nected in the same molecule with different carbon atoms.
The additive (c) 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-R,
I I II II I
H-0 H O 0 0-H
~
where R is hydrocarbyl, and Rl is hydrogen or hydrocarbyl, preferably lower
alkyl,
i.e. (C1-C4). 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, 4-
hydroxy-4-methyl-2-pentanone, or similar ketols or mixture thereof.
In yet another embodiment the fuel additive (c) is a ketone ester, preferably
of the
general formula:
H
I
R-C-C-C-O-R
II I II
0 H 0
where R is hydrocarbyl, preferably lower alkyl, i.e. (C1-C4).
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Typical ketone esters include methylacetoacetate, ethyl acetoacetate and tert-
butyl
acetoacetate. Preferably, such ketone esters have 6 to 8 carbon atoms.
The additive (c) can also be a ring-oxygen-containing heterocyclic compound
and,
preferably, the oxygen-containing heterocycle has a C4 _ C5 ring. More
preferably,
the heterocycle additive has a total of 5 to 8 carbon atoms. The additive can
pref-
erably have the formula (1) or (2) as follows:
R Ri
R R R \ / R
R\i i R \ C i
C-C~ R-C~ ~C-R
R_ C C ~ ,R, i I
i R- / C, 0 ' C \ - R
R 0 R R R
1 2
where R is hydrogen or hydrocarbyl, preferably -CH3, and Rl is -CH3, or -OH,
or
-CH2OH, or CH3CO2CH2-.
A typical heterocyclic additive (c) is tetrahydrofurfuryl alcohol,
tetrahydrofur-
furylacetate, dimethyltetrahydrofurane, tetramethyltetrahydrofurane,
methyltetra-
hydropyrane, 4-methyl-4-oxytetrahydropyrane or similar heterocyclic additives,
or
mixtures thereof.
Component (c) 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 (b) to be used according to the present invention
can
readily be identified by the person skilled in the art. A suitable example of
the etha-
nol 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 (c) should be taken into ac-
count when determining the amount used of component (c). That is, such impuri-
ties 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 (c). 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.
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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
vol-
ume of the motor fuel composition.
Generally, the ethanol (b) 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 (c) 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 (b) and oxygen-containing additive (c)
em-
ployed 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
vol-
ume, and most preferably from 5 to 15 % by volume.
The ratio of ethanol (b) to oxygen-containing additive (c) in the motor fuel
composi-
tion 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 wt.%, more
preferably
no greater than about 5 wt.%.
According to a preferred embodiment of the invention to obtain a motor fuel
suit-
able for the operation of a standard spark ignition internal combustion engine
the
aforesaid hydrocarbon component, ethanol, and additional oxygen-containing com-
ponent 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/m3;
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- 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 80;
- 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 ben-
zene, 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 20 C;
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. 205 C;
- sulfur content of not more than 50mg/kg;
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- resins content of not more than 2mg/ 100m1.
According to a preferred embodiment of the method of the invention the
hydrocar-
bon 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 tem-
perature not lower than -35 C, for at least about one hour. It is a feature of
this in-
vention 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
compo-
sition suitable for operating a standard spark ignition internal combustion
engine
and with a minimal harmful impact on the environment, it is preferable to use
oxy-
gen-containing component(s) originating from renewable raw material(s).
Optionally, a component (d) can be used for further lowering the vapour
pressure of
the fuel mixture of components (a), (b) and (c). An individual hydrocarbon
selected
from a C6 - C12 fraction of aliphatic or alicyclic saturated and unsaturated
hydro-
carbons can be used as component (d). Preferably the hydrocarbon component (d)
is
selected from a Cs-C11 fraction. Suitable examples of (d) are benzene,
toluene, xy-
lene, ethylbenzene, isopropylbenzene, isopropyltoluene, diethylbenzene,
isopropyl-
xylene, tert-butylbenzene, tert-butyltoluene, tert-butylxylene,
cyclooctadiene, cy-
clooctotetraene, limonene, isooctane, isononane, isodecane, isooctene,
myrcene,
allocymene, tert-butylcyclohexane or similar hydrocarbons and mixtures hereof.
Hydrocarbon component (d) 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 (b) and (c) and, optionally also component (d), which
subsequently
can be added to the hydrocarbon component (a) and is also possible to use as
such
as a fuel for a modified spark ignition combustion engine.
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The additive mixture preferably has a ratio of ethanol (b) to additive (c) of
1:150 to
200:1 by volume. According to a preferred embodiment of the additive mixture,
said
mixture comprises the oxygen-containing component (c) in an amount from 0.5 up
to 99.5 % by volume, and ethanol (b) in an amount from 0.5 up to 99.5 % by vol-
5 ume, and component (d) comprising at least one C6 - C12 hydrocarbon, more
prefera-
bly C8-C11 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
etha-
nol (b) to the sum of the other additive components (c)+(d) from 1:200 to
200:1 by
10 volume, more preferable a ratio of ethanol (b) to the sum of the components
(c) + (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 (a) to a desired level by
admix-
15 ing a corresponding portion of the mixture (b), (c), (d) to component (a).
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 (b) and (c), and optionally (d), which mixture
thereafter can
be added to the component (a), or vice versa. In this case a certain amount of
mix-
ing may be required.
EXAMPLES
To prepare the blended motor fuel the following was used as the components
(b), (c),
and (d) :
- fuel grade ethanol purchased in Sweden at Sekab and in the USA from ADM
Corp. and Williams;
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16
- oxygen-containing compounds, individual unsubstituted hydrocarbons and
mixtures hereof purchased in Germany from Merck and in Russia from Lu-
koil.
- Naphtha, which is an oil straight run gasoline containing aliphatic and
alicy-
clic saturated and unsaturated hydrocarbons. Alkylate, which is a hydrocar-
bon fraction consisting almost completely of isoparaffine hydrocarbons ob-
tained in alkylation of isobutene by butanol. Alkylbenzene, which is a mix-
ture of aromatic hydrocarbons obtained in benzene alkylation. Mostly, tech-
nical grade alkylbenzene comprises ethylbenzene, propylbenzene, isopropyl-
benzene, 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) pro-
vides specific CO, (HC + NO) and (PM) standards, while EU Fuel Consumption Di-
rective 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
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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, Q8OK
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,
includ-
ing 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
0.5(RON + 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
pos-
sibility of adjusting the dry vapor pressure equivalent (DVPE) of the ethanol-
containing motor fuel based on winter A92 gasoline.
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The inventive fuel 1-2 contained A92 winter gasoline (a), ethanol (b) and
oxygen-
containing additives (c) and had the following properties for the various
composi-
tions:
A92 : Ethanol : Isobutyl acetate = 88.5 : 4.5 : 7 % by volume
DVPE = 89.0 kPa
0.5(RON + MON) = 89.9
A92 : Ethanol : Isoamyl acetate = 88: 5: 7 % by volume
DVPE = 88.6 kPa
0.5(RON + 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
0.5(RON + MON) = 87.8
A92 : Ethanol : Isoamylpropionate = 87.5 : 5.5 : 7 % by volume
DVPE = 88.7 kPa
0.5(RON + 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
correspon-
ding 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
0.5(RON + MON) = 89.9
A92 : Ethanol : 2,6-dimethyl-4-heptanol = 85 : 8.5 : 6.5 % by volume
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DVPE = 90.0 kPa
0.5(RON + MON) = 90.3
A92 : Ethanol : Diisobutyl ketone = 85 : 7.5 : 7.5 % by volume
DVPE = 90.0 kPa
0.5(RON + MON) = 90.25
The inventive fuel 1-3 contained A92 winter gasoline (a), ethanol (b), oxygen-
containing additives (c) and hydrocarbons C6-C12 (d), and had the following
proper-
ties 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
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DVPE = 90 kPa
0.5(RON + MON) = 91.0
A92 : Ethanol : Isobutyl acetate : Toluene = 82.5 : 9.5 : 0.5 : 7.5 % by
volume
5 DVPE = 90 kPa
0.5(RON + MON) = 90.8
A92 : Ethanol : Isobutanol : Isoamyl alcohol : m-Xylene = 82.5 : 9.2 : 0.2
0.6 : 7.5 % by volume
10 DVPE=90kPa
0.5(RON + 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
15 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
0.5(RON + 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 (a), ethanol (b), and oxygen-
containing
additives (c) and had the following properties for the various compositions:
A98 : Ethanol : Isobutanol= 84 :9 : 7 %o by volume
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DVPE = 88.5 kPa
0.5(RON + MON) = 93.0
A98 : Ethanol : Tert-butylacetate = 84 : 9 : 7 % by volume
DVPE = 89.5 kPa
0.5(RON + 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
0.5(RON + MON) = 92.9
A98 : Ethanol : Diethyl ketone = 85 : 7.5 : 7.5 % by volume
DVPE = 89.0 kPa
0.5(RON + MON) = 92.85
A98 : Ethanol : Methylpropyl ketone = 85 : 7.5 : 7.5 % by volume
DVPE = 89.5 kPa
0.5(RON + MON) = 93.0
A98 : Ethanol : Methylisobutyl ketone = 85 : 7.5 : 7.5 % by volume
DVPE = 89.0 kPa
0.5(RON + 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
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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 = 90.0 kPa
0.5(RON + 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
0.5(RON + MON) = 93.05
The fuel 1-6 contained A98 winter gasoline (a), ethanol (b), oxygen-containing
addi-
tives (c), and C6-Ci2 hydrocarbons (d) and had the following properties for
the vari-
ous compositions:
A98 : Ethanol : Isoamyl alcohol : Isooctane = 80 : 5: 5: 10 % by volume
DVPE = 82.0 kPa
0.5(RON + MON) = 93.2
A98 : Ethanol : Isoamyl alcohol : m-Isopropyl toluene = 78.2 : 6.1 : 6.1 : 9.6
% by volume
DVPE = 81.0 kPa
0.5(RON + MON) = 93.8
A98 : Ethanol : Isobutanol : Naphtha = 80 : 5: 5: 10 % by volume
The boiling point of the naphtha is 100-200 C.
DVPE = 82.5 kPa
0.5(RON + MON) = 92.35
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23
A98 : Ethanol : Isobutanol : Naphtha : m-Isopropyl toluene = 80 : 5 : 5 : 5 5
% by volume
The boiling point of the naphtha is 100-200 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 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) = 933
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=90kPa
0.5(RON + MON) = 93.1
The motor fuel compositions below demonstrate that it might be necessary to
redu-
ce 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
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24
gasoline. In this way, for example, it is possible to transform the winter
grade gaso-
line into the summer grade gasoline. The DVPE level for the summer gasoline is
70
kPa.
A98 : Ethanol : Isobutanol : Isooctane : Naphtha = 60 : 9.5 : 0.5 : 15 : 15 %
by volume
The boiling point of the naphtha is 100-200 C.
DVPE = 70 kPa
0.5(RON + MON) = 92.85
A98 : Ethanol : Isobutanol : Alkylate : Naphtha = 60 : 9.5 : 0.5 : 15 : 15 %
by
volume
The boiling point of the naphtha is 100-200 C.
The boiling point of the alkylate is 100-130 C.
DVPE = 70 kPa
0.5(RON + 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
0.5(RON + 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/km;
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HC (hydrocarbons) 0.280g/km;
NOX (nitrogen oxides) 0.265g/km;
C02 (carbon dioxide) 227.0g/km;
NMHC* 0.276g/km;
5 Fuel consumption, Fc 1/ 100km 9.84
* Non-methane hydrocarbons.
The comparative fuel 1-7 contained A95 winter gasoline and ethanol, and had
the
10 following properties for the various compositions:
A95 : Ethanol = 95 : 5 % by volume
DVPE = 94.9 kPa
0.5(RON + MON) = 91.6
A95 : Ethanol = 90: 10 % by volume (referred to as RFM 1 below)
DVPE = 94.5 kPa
0.5(RON + 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 -7.3%;
NOx +15.5%;
C02 +2.4%;
NMHC* -0.5%;
Fuel consumption, Fc, 1/ 100km +4.7%
"-" represents a reduction in emission, while "+" represents an increase in
emission.
The inventive fuel 1-8 contained A95 winter gasoline (a), ethanol (b) and the
oxygen-
containing additives (c), and had the following properties for the various
composi-
tions:
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A95 : Ethanol : Diisoamyl ether = 86 : 8: 6 % by volume
DVPE = 87.5 kPa
0.5(RON + MON) = 90.6
A95 : Ethanol : Isobutyl acetate = 88 : 5 : 7 % by volume
DVPE = 87.5 kPa
0.5(RON + MON) = 91.85
A95 : Ethanol : Isoamylpropionate = 88 : 5: 7 % by volume
DVPE = 87.0 kPa
0.5(RON + MON) = 91.35
A95 : Ethanol : Isoamylacetate = 88: 5: 7 % by volume
DVPE = 87.5 kPa
0.5(RON + MON) = 91.25
A95 : Ethanol : 2-octanone = 88 : 5 : 7 % by volume
DVPE = 87.0 kPa
0.5(RON + MON) = 90.5
A95 : Ethanol : Tetrahydrofurfuryl alcohol = 88 : 5 : 7 % by volume
DVPE 87.5 kPa
0.5(RON + 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.
A95 : Ethanol : Diisoamyl ether = 87 : 9: 4 % by volume
DVPE = 90.0 kPa
0.5(RON + MON) = 91.0
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A95 : Ethanol : Isoamyl acetate = 88 : 7: 5 % by volume
DVPE = 90.0 kPa
0.5(RON + MON) = 91.3
A95 : Ethanol : Tetrahydrofurfuryl alcohol = 88 : 7: 5 % by volume
DVPE = 90.0 kPa
0.5(RON + MON) = 90.8
The fuel 1-9 contained A95 winter gasoline (a), ethanol (b), the oxygen-
containing
additives (c), and C6-C12 hydrocarbons (d) and had the following properties
for the
various compositions:
A95 : Ethanol : Isoamyl alcohol : Alkylate = 83.7 : 5 : 2 : 9.3 % by volume
The boiling temperature of the alkylate is 100-130 C
DVPE = 88.0 kPa
0.5(RON + MON) = 91.65
A95 : Ethanol : Isoamyl alcohol : Naphtha = 83.7 : 5: 2: 9.3% by vol.
The boiling temperature of the naphtha is 100-200 C
DVPE = 88.5 kPa
0.5(RON + MON) = 90.8
A95 : Ethanol : Isobutyl acetate : Alkylate = 81 : 5: 5 9 % by volume
The boiling temperature of the alkylate is 100-130 C
DVPE = 87.0 kPa
0.5(RON + MON) = 92.0
A95 : Ethanol : Isobutyl acetate : Naphtha = 81 : 5: 5 9 % by volume
The boiling temperature of the naphtha is 100-200 C
DVPE = 87.5 kPa
0.5(RON + 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
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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
0.5(RON + MON) = 92.1
A95 : Ethanol : Isobutanol : Isoamyl alcohol : Naphtha = 80 : 9.2 : 0.2 : 0.6
:
10 % by volume
The boiling temperature of the naphtha is 100-200 C
DVPE = 90.0 kPa
0.5(RON + 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
redu-
ce 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 gaso-
line into the summer grade gasoline. The DVPE level for the summer gasoline is
70
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 C.
DVPE=70.OkPa
0.5(RON + MON) = 91.8
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A95 : Ethanol : Tert-butyl acetate : Naphtha = 60 : 9: 1 : 30 % by volume
The boiling temperature of the naphtha is 100-200 C.
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
etha-
nol, 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 for-
mulation demonstrates the possibility of decreasing the DVPE, increasing the
oc-
tane 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 1). The motor fuel composition has the following properties:
density at 15 C, according to ASTM D 4052 749.2 kg /m3;
initial boiling point, according to ASTM D 86 29 C;
vaporizable portion - 70 C 47.6 % by volume;
vaporizable portion - 100 C 55.6 % by volume;
vaporizable portion - 150 C 84.2 % by volume;
vaporizable portion - 180 C 97.5 % by volume;
final boiling point 194.9 C;
evaporation residue 1.3 % by volume;
loss by evaporation 1.6 % by volume;
oxygen content, according to ASTM D4815 3.7%w/w;
acidity, according to ASTM D 1613
weight% HAc 0.004;
pH, according to ASTM D 1287 6.6;
sulfur content, according to ASTM D 5453 18mg/kg;
gum content, according to ASTM D381 1 mg/ l00m1;
water content, according to ASTM D6304 0.03% w/w;
aromatics, according to SS 155120,
including benzene 30.2 % by volume;
benzene alone, according to EN 238 0.7 % by volume;
DVPE, according to ASTM D 5191 89.OkPa;
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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
5 method EU 2000 NEDC EC 98/69 and the following results, as compared to
winter
A95 gasoline, were obtained:
CO -21%;
HC -9%;
10 NOx +12.8%;
C02 +2.38%;
NMHC -6.4%;
Fuel consumption, Fc 1/ 100km +3.2%
15 The fuel formulations 1-1 to 1-10 showed reduced DVPE over the tested
ethanol-
containing motor fuels based on summer grade gasoline. Similar results are ob=
tained when other oxygen-containing compounds of this invention are
substituted
for the additives of the examples 1-1 to 1-10.
20 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
25 mixing devices.
It was established the possibility of employing an additive mixture of the
oxygen-
containing additive other than ethanol (c) and ethanol (b) for formulating the
etha-
nol-containing motor fuels for standard internal combustion spark ignition
engines
30 meeting standard requirements for gasolines, both regarding vapour pressure
and
anti-knock stability.
The fuel compositions below demonstrate such a possibility.
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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
0.5(RON + MON) = 90.15
A95 : Ethanol : Isoamyl alcohol = 86 : 7,0 : 7.0 % by volume
DVPE = 89.3 kPa
0.5(RON + MON) = 92.5
A98 : Ethanol : Isoamyl alcohol = 85 : 7.5 : 7.5 % by volume
DVPE = 86.5 kPa
0.5(RON + 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
gasoli-
nes, 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
gasoli-
nes 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 C6-C12 hydrocarbons (component (d)). The compositions below demon-
strate the effect achieved by means of the invention.
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32
An additive mixture comprising 40 % by volume of ethanol, 10 % by volume of
iso-
butanol and 50 % by volume of isopropyltoluene was mixed with winter gasoline
with DVPE not higher than 90 kPa. The various compositions obtained had the
fol-
lowing properties:
A92 : Ethanol: Isobutanol : Isopropyltoluene = 85 : 6: 1.5 : 7.5 % by volume
DVPE = 84.9 kPa
0.5(RON + MON) = 93.9
A95 : Ethanol: Isobutanol : Isopropyltoluene = 80 : 8: 2: 10 % by volume
DVPE = 84.0 kPa
0.5(RON + MON) = 94.1
A98 : Ethanol: Isobutanol : Isopropyltoluene = 86 : 5.6 : 1.4 : 7 % by volume
DVPE = 85.5 kPa
0.5(RON + MON) = 93.8
Similar results were obtained when other oxygen-containing compounds and also
C6-C12 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
etha-
nol-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,
Q8OK,
and Preem, were used.
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The source gasoline comprised aliphatic and alicyclic C4-C12 hydrocarbons,
includ-
ing 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 win-
ter A 92 and A98 gasolines, respectively, demonstrated similar behaviour.
The following fuels 2-2 and 2-3 demonstrate the possibility of adjusting the
dry va-
pour 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
0.5(RON + 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 (a), ethanol (b), and the oxygen-
containing additives (c) and had the followi.ng properties for the various
composi-
tions:
A92 : Ethanol : Isoamyl alcohol = 85 : 6.5 : 6.5 % by volume
DVPE = 69.8 kPa
0.5(RON + MON) = 90.3
A92 : Ethanol : Isobutanol = 80: 10: 10 % by volume
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DVPE = 67.5 kPa
0.5(RON + MON) = 90.8
A92 : Ethanol : Diethylcarbinol = 85 : 6.5 : 6.5 % by volume
DVPE = 69.6 kPa
0.5(RON + MON) = 90.5
A92 : Ethanol : Diisobutyl ketone = 85.5 : 7.5 : 7 % by volume
DVPE = 69.0 kPa
0.5(RON + MON) = 90.0
A92 : Ethanol : Diisobutyl ethter = 85 : 8: 7 /O 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
0.5(RON + MON) = 88.5
A92 : Ethanol : Isobutylacetate = 88: 5: 7 % by volume
DVPE = 69.5 kPa
0.5(RON + 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
0.5(RON + MON) = 90.6
A92 : Ethanol : Di-n-butyl ether = 85 : 9 : 6 % by volume
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DVPE = 70.0 kPa
0.5(RON + MON) = 89.2
A92 : Ethanol : Diisobutyl ketone = 85 : 8:' :'by volume
5 DVPE = 70.0 kPa
0.5(RON + MON) = 90.4
The fuel 2-3 contained A92 summer gasoline (a), ethanol (b), the oxygen-
containing
additives (c), and C6-Ci2 hydrocarbons (d) and had the following properties
for the
10 various compositions:
A92 : Ethanol : Methylethyl ketone : Isooctane = 80 : 9.5 : 0.5 : 10 % by vol-
ume
DVPE = 69.0 kPa
15 0.5(RON + MON) = 91.0
A92 : Ethanol : Isobutanol : Isooctane = 80 : 9.5 : 0.5 : 10 % by volume
DVPE = 69.0 kPa
0.5(RON + MON) = 91.1
A92 : Ethanol : Isobutanol : Isononane = 80 : 9.5 : 0.5: 10 % by volume
DVPE = 68.8 kPa
0.5(RON + MON) = 91.0
A92 : Ethanol : Isobutanol : Isodecane = 80 : 9.5 : 0.5 : 10 % by volume
DVPE = 68.5 kPa
0.5(RON + MON) = 90.8
A92 : Ethanol : Isobutanol : Isooctene = 80 : 9.5 : 0.5: 10 % by volume
DVPE = 68.9 kPa
0.5(RON + 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
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A92 : Ethanol : Isobutanol : Naphtha = 80 : 9.5 : 0.5: 10 % by volume
The boiling temperature for the naphtha is 100-200 C
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 C
DVPE = 67.5 kPa
0.5(RON + MON) = 90.9
A92 : Ethanol : Isobutanol : Naphtha : Isopropyltoluene = 80 : 9.5 : 0.5 : 5:
5
% by volume
The boiling temperature for the naphtha is 100-200 C
DVPE=67.5kPa
0.5(RON + 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
0.5(RON + MON) = 90.85
A92 : Ethanol : Isobutanol : Tert-butylbenzene = 82.5 : 9.5 : 0.5 : 7.5 % by
volume
DVPE = 70.0 kPa
0.5(RON + MON) = 91.5
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A92 : Ethanol : Isobutanol : Isoamyl alcohol : Naphtha : Tert-butyltoluene =
82.5 : 9.2 : 0.2 : 0.6 : 5: 2.5 % by volume
DVPE=70.0kPa
0.5(RON + MON) = 91.1
The following fuels 2-5 and 2-6 demonstrate the possibility of adjusting the
dry va-
pour 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
0.5(RON + MON) = 93.3
A98 : Ethanol = 90: 10 % by volume
DVPE = 76.0 kPa
0.5(RON + MON) = 93.7
The fuel 2-5 contained A98 summer gasoline (a), ethanol (b) and the oxygen-
containing additives (c), and had the following properties for the various
composi-
tions:
A98 : Ethanol : Isobutanol = 85 : 7.5 : 7.5 % by volume
DVPE = 69.5 kPa
0.5(RON + MON) = 93.5
A98 : Ethanol : Diisobutyl ketone = 83 : 9.5 : 7.5 % by volume
DVPE = 69.0 kPa
0.5(RON + MON) = 93.9
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A98 : Ethanol : Isobutyl acetate = 88: 5: 7 % by volume
DVPE = 69.5 kPa
0.5(RON + 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
0.5(RON + MON) = 93.7
A98 : Ethanol : Tert-pentanol = 90 : 5 : 5 % by volume
DVPE=70.OkPa
0.5(RON + MON) = 93.8
The fuel 2-6 contained A98 summer gasoline (a), ethanol (b), the oxygen-
containing
additives (c), and C6-C12 hydrocarbons (d) 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
0.5(RON + 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
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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
0.5(RON + 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 va-
pour 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
fol-
lowing results:
CO (carbon monoxide) 2.198g/km;
HC (hydrocarbons) 0.245g/km;
NOX (nitrogen oxides) 0.252g/km;
CO2 (carbon dioxide) 230.0g/km;
NMHC* 0.238g/km;
Fuel consumption, Fc 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:
A95 : Ethanol = 95%: 5 % by volume
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DVPE = 75.5 kPa
0.5(RON + MON) = 90.9
A95 : Ethanol = 90%: 10 % by volume (also referred to as RFM2 below)
5 DVPE = 75.0 kPa
0.5(RON + MON) = 92.25
The testing of the reference fuel mixture (RFM 2) demonstrated the following
re-
sults, as compared to summer A95 gasoline:
CO -9.1%;
HC -4.5%;
NOx +7.3%;
C02 +4.0%;
NMHC* -4.4%;
Fuel consumption, F, 1 J 100km +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:
A95 : Ethanol : Isoamyl alcohol = 85 : 7.5 : 7.5 % by volume
DVPE = 68.5 kPa
0.5(RON + MON) = 92.2
A95 : Ethanol : Diisoamyl ether = 86 : 8 6 % by volume
DVPE=66.5kPa
0.5(RON + MON) = 90.2
A95 : Ethanol : Isobutylacetate = 88: 5 7 % by volume
DVPE = 67.0 kPa
0.5(RON + MON) = 92.0
A95 : Ethanol : Tert-butanol = 88 : 5 : 7 % by volume
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DVPE = 68.4 kPa
0.5(RON +' MON) = 92.6
A95 : Ethanol : Tert-pentanol = 90: 5: 5 /a by volume
DVPE = 68.5 kPa
0.5(RON + MON) = 92.2
A95 : Ethanol : Isopropanol = 80 : 10 : 10 % by volume
DVPE = 68.5 kPa
0.5(RON + MON) = 92.8
A95 : Ethanol : 4-methyl-2-pentanol = 85 : 8 : 7 % by volume
DVPE = 66.0 kPa
0.5(RON + MON) = 91.0
A95 : Ethanol : Diethyl ketone = 85 : 8 : 7 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 92.2
A95 : Ethanol : Trimethylcyclohexanone = 85 : 8: 7 % by volume
DVPE = 67.0 kPa
0.5(RON + MON) = 91.8
A95 : Ethanol : Methyltertamyl ether = 80 : 8: 12 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 93.8
A95 : Ethanol : n-Butylacetate = 87: 6.5 : 6.5 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 90.1
A95 : Ethanol : Isobutylisobutyrate = 90 : 5: 5 % by volume
DVPE = 68.5 kPa
0.5(RON + MON) = 90.0
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A95 : Ethanol : Methylacetoacetate = 85 : 7: 8 % by volume
DVPE = 68.5 kPa
0.5(RON + 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.
A95 : Ethanol : 4-methyl-2-pentanol = 85: 10: 5 % by volume
DVPE = 70.0 kPa
0.5(RON + MON) = 91.6
A95 : Ethanol : Isobutylisobutyrate = 90 : 6 : 4 % by volume
DVPE=70.OkPa
0.5(RON + MON) = 90.5
The fuel 2-9 contained A95 summer gasoline (a), ethanol (b), the oxygen-
containing
additives (c), and C6-C12 hydrocarbons (d) and had the following properties
for the
various compositions:
A95 : Ethanol : Tert-pentanol: Alkylbenzene = 80 : 7: 4: 9 % by volume
DVPE = 67.5 kPa
0.5(RON + MON) = 93.6
A95 : Ethanol : Tert-butanol: Alkylbenzene = 80 : 7 : 4 : 9 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 93.8
A95 : Ethanol : Propanol : Xylene = 80 : 9.5 : 0.5: 10 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 93.1
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A95 : Ethanol : Diethylketone : Xylene = 80 : 9.5 : 0.5: 10 % by volume
DVPE = 68.0 kPa
0.5(RON + MON) = 93.2
A95 : Ethanol : Isobutanol : Naphtha : Isopropyltoluene = 80 : 9.5 : 0.5 : 5 5
% by volume
The boiling temperature for the naphtha is 100-170 C
DVPE = 68.0 kPa
0.5(RON + MON) = 92.4
A95 : Ethanol : Isobutanol : Naphtha : Alkylate = 80 : 9.5 : 0.5 : 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
0.5(RON + 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
7.5 % by volume
DVPE = 70.0 kPa
0.5(RON + 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
0.5(RON + MON) = 92.1
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The fuel formulation 2-10 contained 81.5% by volume of A95 summer gasoline,
8.5% 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 15 C, according to ASTM
D4052 754.lkg /m3;
initial boiling point, according to
ASTM D 86 26.6 C;
vaporisable portion - 70 C 45.2 % by volume;
vaporisable portion - 100 C 56.4 % by volume;
vaporisable portion - 150 C 88.8 % by volume;
vaporisable portion - 180 C 97.6 % by volume;
final boiling point 186.3 C;
evaporation residue 1.6 % by volume;
loss by evaporation 0.1 % by volume;
oxygen content, according to ASTM
D4815 3.56% w/w;
acidity, according to ASTM D 1613
weight% HAc 0.007;
pH, according to ASTM D 1287 8.9;
sulfur content, according to ASTM D 5453 16mg/kg;
gum content, according to ASTM D381 < 1mg/ 100m1;
water content, according to ASTM D6304 0.12% w/w;
aromatics, according to SS 155120,
including benzene 30.3 % by volume;
benzene alone, according to EN 238 0.8 % by volume;
DVPE, according to ASTM D 5191 68.5kPa;
anti-knock index 0.5(RON+MON), according
to ASTM D 2699-86 and ASTM D 2700-86 92.7
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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:
5 CO -0.18%
HC -8.5%;
NOx +5.3%;
CO2 +2.8%;
NMHC -9%;
10 Fuel consumption, Fc, 1/ 100km +3.1%
The fuel formulations 2-1 to 2-10 showed reduced DVPE over the tested ethanol-
containing motor fuels based on summer grade gasoline. Similar results are ob-
tained when other oxygen-containing additives of the invention are substituted
for
15 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
composi-
tion, initially gasoline was mixed with ethanol, to which mixture was. then
added
the corresponding oxygen-containing additive. The motor fuel composition
obtained
20 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 com-
25 pounds other than ethanol for preparation of the ethanol-containing
gasolines was
accomplished with summer grade gasolines. The fuel compositions below demon-
strate 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 alco-
hol, and 60 % by volume of naphtha boiling at temperatures between 100-170 C.
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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
compo-
sitions higher than the requirements of the standards for DVPE of the summer
gra-
de 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 100-170 C.
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 ga-
solines, is of substantial importance. The ratio between the components of the
ad-
ditive 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
mix-
tures 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
iso-
butanol 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 vol-
ume
DVPE = 70.0 kPa
0.5(RON + MON) = 90.3
A95 : 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=70.0kPa
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0.5(RON + MON) = 94.5
An additive mixture comprising 25 % by volume of ethanol, 60 % by volume of
iso-
amyl alcohol, and 15 % by volume of isobutanol was mixed with summer grade ga-
soline. The compositions obtained had the following properties:
A92 : Ethanol : Isoamyl alcohol : Isobutanol = 80 : 5: 12 : 3 % by volume
DVPE = 66.0 kPa
0.5(RON + MON) = 88.6
A95 : Ethanol : Isoamyl alcohol : Isobutanol = 84 : 4 : 9.6 : 2.4 % by volume
DVPE = 65.5 kPa
0.5(RON + MON) = 91.3
A98 : Ethanol : Isoamyl alcohol : Isobutanol = 86 : 3.5 : 8.4 : 2.1 % by vol-
ume
DVPE = 65.0 kPa
0.5(RON + MON) = 93.0
Similar results were obtained when other oxygen-containing compounds (c) and
also C6-C12 hydrocarbons (d) 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
com-
pound 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
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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,
A95,
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 C5-C12 hydrocarbons, in-
cluding 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
0.5(RON + MON) = 89.0
A92 : Ethanol =-90 : 10 % by volume
DVPE = 55.4 kPa
0.5(RON + MON) = 90.1
The fuel 3-2 contained US A92 summer gasoline, ethanol, and the oxygen-
containing 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
0.5(RON + MON) = 89.6
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A92 : Ethanol : Isoamyl propionate = 82 : 8: 10 % by volume
DVPE = 47.0 kPa
0.5(RON + MON) = 89.9
A92 : Ethanol : 2-Ethylhexanol = 82 : 8: 10 % by volume
DVPE = 47.8 kPa
0.5(RON + MON) = 89.2
A92 : Ethanol : Tetrahydrofurfuryl alcohol = 82 : 7: 10 % by volume
DVPE=47.8kPa
0.5(RON + MON) = 89.3
A92 : Ethanol : Cyclohexanone = 82 : 7: 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
0.5(RON + MON) = 90.6
A92 : Ethanol : Methoxytoluene = 82 : 8: 10 % by volume
DVPE = 46.5 kPa
0.5(RON + MON) = 90.8
A92 : Ethanol : Methylbenzoate = 82 : 8: 10 % by volume
DVPE = 46.0 kPa
0.5(RON + 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
correspon-
ding gasoline. The DVPE level for the US summer grade gasoline is 7 psi, which
cor-
responds to 48.28 kPa.
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A92 : Ethanol : Isoamyl alcohol = 83 : 9 8 % by volume
DVPE = 48.2 kPa
0.5(RON + MON) = 89.8
5 A92 : Ethanol : Methoxytoluene = 84 : 8 8 % by volume
DVPE = 48.2 kPa
0.5(RON + MON) = 90.5
A92 : Ethanol : Methylbenzoate = 85: 8 7 % by volume
10 DVPE=48.2kPa
0.5(RON + MON) = 90.1
The fuel 3-3 contained US A92 summer gasoline (a), ethanol (b), the oxygen-
containing additives (c), and C6-Ci2 hydrocarbons (d) and had the following
proper-
15 ties 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 100-2001C
20 DVPE = 47.8 kPa
0.5(RON + MON) = 89.5
A92 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : m-Isopropyltoluene = 75
9.2 : 0.3 : 0.1 : 15.4 % by volume
25 DVPE=47.OkPa
0.5(RON + MON) = 90.5
A92 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Isooctane = 75 : 9.2 :
0.3
0.1 : 15.4 % by volume
30 DVPE = 47.8 kPa
0.5(RON + 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
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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
corres-
ponds 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 C
DVPE=48.2kPa
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
0.5(RON + 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
0.5(RON + 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:
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52
A98 : Ethanol = 95 : 5 % by volume
DVPE = 56.3 kPa
0.5(RON + MON) = 93.0
A98 : Ethanol = 90: 10 % by volume
DVPE = 55.8 kPa
0.5(RON + MON) = 93.6
The fuel 3-5 contained US A98 summer gasoline (a), ethanol (b) and the oxygen-
containing additives (c), and had the following properties for the various
composi-
tions:
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
0.5(RON + MON) = 93.7
The fuel 3-6 contained US A98 summer gasoline (a), ethanol (b), the oxygen-
containing additives (c), and C6-C12 hydrocarbons (d) and had the following
proper-
ties 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 100-200 C
DVPE = 48.2 kPa
0.5(RON + MON) = 93.3
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A98 : Ethanol : Isoamyl 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 : Isoamyl 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 = 75
:
9.2 : 0.3 : 0.1 : 8.4 : 7% by volume
The boiling temperature for the naphtha is 100-200 C
DVPE=48.2kPa
0.5(RON + MON) = 93.6
A98 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Naphtha : m-Isopropyl
toluene = 75 : 9.2 : 0.3 : 0.1 : 10.4 : 5% by volume
The boiling temperature for the naphtha is 100-200 C
DVPE = 48.0 kPa
0.5(RON + MON) = 93.7
A98 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Naphtha : Alkylate = 75 :
9.2 : 0.3 : 0.1 : 7.9 : 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
0.5(RON + MON) = 93.6
The following fuels demonstrated the possibility of adjusting the dry vapour
pres-
sure equivalent (DVPE) of the ethanol-containing motor fuel based on US summer
A95 gasoline.
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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
revo-
lutions/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;
C02 (carbon dioxide) 232.6g/km;
NMHC* 0.258g/km;
Fuel consumption, F,, 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
0.5(RON + MON) = 91.5
A95 : Ethanol = 90: 10 % by volume
DVPE = 54.8 kPa
0.5(RON + MON) = 92.0
Testing of the reference gasoline-alcohol mixture (RFM3) comprising 90 % by
volu-
me of US A95 summer grade gasoline and 10 % by volume of ethanol performed on
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a 1987 Volvo 240 DL with a B230F, 4-cylinder, 2.32 litre engine (No. LG4F20-
87) in ac-
cordance with the standard test method EU 2000 NEDC EC 98/69 demonstrated
the following results, as compared to summer US A95 gasoline:
5 CO -12.5%;
HC -4.8%;
NOx +2.3%;
C02 +3.7%;
NMHC* -4.0%;
10 Fuel consumption, F, 1/ 100km. +3.1%
"-" represents a reduction in emission, while "+" represents an increase in
emission.
The' fuel 3-8 contained US A95 summer gasoline, ethanol and the oxygen-
15 containing additives, and had the following properties for the various
compositions:
A95 : Ethanol : Isoamyl alcohol = 83 : 8.5 : 8.5 % by volume
DVPE = 47.0 kPa
0.5(RON + MON) = 91.7
A95 : Ethanol : n-Amyl acetate = 80: 10: 10 % by volume
DVPE = 47.0 kPa
0.5(RON + MON) = 91.8
A95 : Ethanol : Cyclohexylacetate = 80 : 10 : 10 % by volume
DVPE = 46.7 kPa
0.5(RON + MON) = 92.0
A95 : Ethanol : Tetramethyltetrahydrofurane = 80 : 12 : 8 % by volume
DVPE = 47.0 kPa
0.5(RON + MON) = 92.6
A95 : Ethanol : Methyltetrahydropyrane = 80 : 15 : 5 % by volume
DVPE = 46.8 kPa
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56
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 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
corres-
ponds to 48.28 kPa.
A95 : Ethanol : Isoamyl alcohol = 84 : 8.5 : 7.5 % by volume
DVPE = 48.2 kPa
0.5(RON + MON) = 91.7
A95 : Ethanol : Phenylacetate = 82.5 : 10 : 7.5 % by volume
DVPE=48.2kPa
0.5(RON + MON) = 92.3
A95 : 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 (a), ethanol (b), the oxygen-
containing additives (c), and C6-C12 hydrocarbons (d) and had the following
proper-
ties for the various compositions:
A95 : 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
A95 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Isooctane = 75 : 9.2 :
0.3
0.1 : 15.4 % by volume
DVPE = 47.0 kPa
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0.5(RON + MON) = 92.2
A95 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : m-Isopropyltoluene = 75
9.2 : 0.3 : 0.1 : 15.4 % by volume
DVPE = 46.8 kPa
0.5(RON + MON) = 93.0
A95 : Ethanol : Tetrahydrofurfuryl alcohol : Cyclooctatetraene = 80 : 9.5 :
0.5
% by volume
10 DVPE=46.6kPa
0.5(RON + MON) = 92.5
A95 : Ethanol : 4-Methyl-4-oxytetrahydropyrane : Allocymene = 80 : 9.5= : 0.5
10 % by volume
DVPE=46.7kPa
0.5(RON + 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
corres-
ponds to 48.28 kPa.
A95 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Naphtha = 76.5 : 9.2 :
0.3
0.1 : 7: 6,9 % by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 48.2 kPa
0.5(RON + MON) = 91.7
A95 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : Naphtha : Isooctane =
76.5 : 9.2 : 0.3 : 0.1 : 7: 6.9 % by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE=48.2kPa
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58
0.5(RON + MON) = 92.2
A95 : Ethanol : Isoamyl alcohol : Isobutyl alcohol : m-Isopropyltoluene = 77
9.2 : 0.3 : 0.1 : 13.4 % by volume
DVPE = 48.2 kPa
0.5(RON + 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 C, and 3 % by volume of isopropyltoluene. Formulation 3-10 was tested to
demonstrate how the invention enables the production of ethanol-containing
gaso-
line 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
se-
cures 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 774.9kg /m3;
initial boiling point, according to
ASTM D 86 36.1 C;
vaporisable portion - 70 C 33.6 % by volume;
vaporisable portion - 100 C 50.8 % by volume;
vaporisable portion - 150 C 86.1 % by volume;
vaporisable portion - 190 C 97.0 % by volume;
final boiling point 204.8 C;
evaporation residue 1.5 % by volume;
loss by evaporation 1.5 % by volume;
oxygen content, according to ASTM
D4815 3.37% w/w;
acidity, according to ASTM D 1613
weight% HAc 0.007;
pH, according to ASTM D 1287 7.58;
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59
sulfur content, according to ASTM D 5453 47mg/kg;
gum content, according to ASTM D381 2.8mg/ 100m1;
water content, according to ASTM D6304 0.02% w/w;
aromatics, according to SS 155120,
including benzene 31.2 % by volume;
benzene alone, according to EN 238 0.7 % by volume;
DVPE, according to ASTM D 5191 48.OkPa;
anti-knock index 0.5(RON+MON), according
to ASTM D 2699-86 and ASTM D 2700-86 92.2
The motor fuel Formulation 3-10 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 source US A95 summer gasoline:
CO -15.1%
HC -5.6%;
NOx +0.5%;
C02 unchanged;
NMHC -4.5%;
Fuel consumption, Fc, 1/ 100km unchanged.
Similar results were obtained when the other oxygen-containing compounds sub-
stituted 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 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.
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-
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ternal combustion spark ignition engines based on summer grade gasolines
meeting
US standards. Adding Cs-C12 hydrocarbons to the composition of the additive
mix-
ture 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.
5
The additive mixture comprising 60 % by volume of ethanol, 32 % by volume of
iso-
amyl 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
A95 : Ethanol : Isoamyl alcohol : Isobutanol = 85 : 9: 4.8: 1.2 % by volume
DVPE = 51.0 kPa
0.5(RON + MON) = 91.8
A98 : Ethanol : Isoamyl alcohol : Isobutanol = 80 : 12 : 6.4: 1.6 % by volume
DVPE = 52.0 kPa
0.5(RON + 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
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0.5(RON + MON) = 90.0
A95 : Ethanol : Methylisobutyl ketone = 84 : 8: 8 % by volume
DVPE=48.6kPa
0.5(RON + MON) = 91.7
A98 : Ethanol : Methylisobutyl ketone = 82 : 9 : 9 % by volume
DVPE = 49.7 kPa
0.5(RON + MON) = 93.9
The foregoing examples demonstrate the possibility of a partial lowering of
the ex-
cess vapour pressure by about 80% of the excess vapour pressure of gasoline in-
duced 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 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 C and 20% by volyme of isopropyltoluene.
Similar results were obtained when other oxygen-containing compounds and C6-
C12
hydrocarbons of this invention were used in the proportion established by this
in-
vention 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.
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62
Moreover, the additive mixture comprising ethanol, the oxygen-containing compo-
und other than ethanol, and C6-C12 hydrocarbons in the proportion and composi-
tion 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-5 191 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, Q8OK 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
15
% 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 (GC). The
ob-
tained 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:
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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 : GC : Ethanol= 80.75: 14.25 : 5% by volume
DVPE = 115.5 kPa
0.5(RON + MON) = 89.4
A92 : GC : Ethanol= 76.5: 13.5: 10 % by volume
DVPE = 115.0 kPa
0.5(RON + MON) = 90.6
The inventive fuel 4-2 contained A92 winter gasoline, gas condensate (GC),
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
0.5(RON + MON) = 90.35
A92 : GC : Ethanol : 2,5 Dimethyltetrahydrofuran = 68 : 12 : 10 : 10 % by
volume
DVPE = 110.0 kPa
0.5(RON + MON) = 90.75
A92 : GC : Ethanol : Propanol = 68: 12: 12 : 8 % by volume
DVPE = 109.5 kPa
0.5(RON + MON) = 90.0
A92 : GC : Ethanol : Diisopropylcarbinol = 72 : 13 : 7.5 : 7.5 % by volume
DVPE = 109.0 kPa
0.5(RON + MON) = 90.3
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A92 : GC : Ethanol : Acetophenone = 72: 13 : 9: 6 % by volume
DVPE = 110.0 kPa
0.5(RON + MON) = 90.8
A92 : GC : Ethanol : Isobutylpropionate = 75 : 13 : 5: 7 % by volume
DVPE = 109.2 kPa
0.5(RON + MON) = 90.0
The fuel 4-3 contained winter A92 gasoline, gas condensate (GC), ethanol, the
oxy-
gen-containing additive and C6-C12 hydrocarbons and had the following
properties
for the various compositions:
A92 : GC : Ethanol : Isobutanol : Isopropylbenzene = 68 : 12 : 9.5 : 0.5 : 10
% by volume
DVPE = 108.5 kPa
0.5(RON + MON) = 91.7
A92 : GC : Ethanol : Tert-butylethyl ether : Naphtha = 68 : 12 : 9.5 : 0.5 :
10
% by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 108.5 kPa
0.5(RON + MON) = 90.6
A92 : GC : Ethanol : Isoamylmethyl ether : Toluene = 68 : 12 : 9.5 : 0.5 : 10
% by volume
DVPE = 107.5 kPa
0.5(RON + 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 : GC : Ethanol : Isoamyl alcohol : Naphtha : Alkylate = 55: 10 : 9.5 : 0.5
: 12.5: 12.5 % by volume
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The boiling temperature for the naphtha is 100-200 C.
The boiling temperature for the alkylate is 100-130 C.
DVPE = 90.0 kPa
0.5(RON + MON) = 90.6
5
A92 : GC : Ethanol : Isoamyl alcohol : Naphtha : Ethylbenzene = 55 : 10 : 9.5
: 0.5: 15: 10 % by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 89.8 kPa
10 0.5(RON + MON) = 90.9
A92 : GC : Ethanol : Isoamyl alcohol : Naphtha : Isopropyltoluene = 55 : 10 :
9.5 : 0.5 : 20 : 5% by volume
The boiling temperature for the naphtha is 100-200 C.
15 DVPE = 90.0 kPa
0.5(RON + 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
20 85 % by volume of winter A98 gasoline and about 15 % by volume of gas
conden-
sate.
The gasoline comprising 85 % by volume of winter A98 gasoline and 15 % by vol-
ume of gas condensate (GC) had the following specification:
25 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
0.5(RON + MON) = 93.1
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A98 : GC : Ethanol = 76.5: 13.5: 10 % by volume
DVPE = 114.8 kPa
0.5(RON + MON) = 94.0
The inventive fuel 4-5 contained A98 winter gasoline, gas condensate (GC) and
the
oxygen-containing additives and had the following properties for the various
compo-
sitions:
A98 : GC : Ethanol : Isoamyl alcohol = 74 :13 : 6.5 : 6.5 % by volume
DVPE = 109.6 kPa
0.5(RON + 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 : GC : 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
oxygen-
containing additives, and C6-C12 hydrocarbons (d) 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 volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 107.4 kPa
0.5(RON + MON) = 93.8
A98 : GC : Ethanol : Ethylisobutyl ether : Myrzene = 72 : 13 : 9.5 : 0.5 : 5 %
by volume
DVPE = 110.0 kPa
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0.5(RON + 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
re-
duction 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 : 0.5
: 12.5 : 12.5 % by volume
The boiling temperature for the naphtha is 100-200 C.
The boiling temperature for the alkylate is 100-130 C.
DVPE = 89.8 kPa
0.5(RON + MON) = 94.0
A92 : GC : Ethanol : Isoamyl alcohol : Naphtha : Isopropylbenzene = 55: 10:
9.5 : 0.5 : 15 : 10 % by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 89.6 kPa
0.5(RON + MON) = 94.2
A92 : GC : Ethanol : Isobutanol : Naphtha : Isopropyltoluene = 55: 10: 5: 5
: 20: 5 % by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 88.5 kPa
0.5(RON + 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
85 % by volume of winter A95 gasoline and about 15 % by volume of gas conden-
sate.
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The gasoline comprising 85 % by volume of winter A98 gasoline and 15 % by vol-
ume 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:
A95 : GC : Ethanol = 80.75: 14.25: 5 % by volume
DVPE = 115.0 kPa
0.5(RON + MON) = 91.7
A95 : GC : Ethanol = 76.5: 13.5: 10 % by volume
DVPE = 114.5 kPa
0.5(RON + 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%
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69
HC -7.3%;
NOx +12.1%;
C02 +1.1%;
NMHC -5.3%;
Fuel consumption, Fc, 1/ 100km +2.62%.
The inventive fuel 4-8 contained A95 winter gasoline, gas condensate (GC),
ethanol
and the oxygen-containing additives and had the following properties for the
vari-
ous compositions:
A95 : GC : Ethanol : Isoamyl alcohol = 74 : 13 : 6.5 : 6.5 % by volume
DVPE = 109.1 kPa
0.5(RON + MON) = 92.0
A95: GC : Ethanol : Phenol = 72: 13 : 8: 7% by volume
DVPE = 107.5 kPa
0.5(RON + MON) = 92.6
A95 : GC : Ethanol : Phenyl acetate = 68: 12: 10: 10 % by volume
DVPE = 106.0 kPa
0.5(RON + MON) = 92.8
A95 : GC : Ethanol : 3-Hydroxy-2-butanone = 68: 12: 10: 10 % by volume
DVPE = 108.5 kPa
0.5(RON + MON) = 91.6
A95 : GC : Ethanol : Tert-butylacetoacetate = 68 : 12 : 10 : 10 % by volume
DVPE = 108.0 kPa
0.5(RON + MON) = 92.2
A95 : GC : Ethanol : 3,3,5-Trimethylcyclohexanone = 71 : 12 : 9 : 8 % by
volume
DVPE = 108.5 kPa
0.5(RON + MON) = 91.6
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The fuel 4-9 contained A95 winter gasoline, gas condensate (GC), ethanol, the
oxy-
gen-containing additives, and C6-C12 hydrocarbons (d) and had the following
prop-
erties for the various compositions:
5 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 100-200 C.
DVPE = 107.0 kPa
0.5(RON + MON) = 92.1
A95 : GC : Ethanol: Isobutanol : Cyclooctatetraene = 72 : 13 : 9.5 : 0.5 : 5 %
by volume
DVPE = 108.5 kPa
0.5(RON + MON) = 92.6
The motor fuel compositions below demonstrate that the invention enables the
re-
duction of the excess vapour pressure equivalent (DVPE) of the non-standard
gaso-
line to the level of the corresponding standard gasoline. The DVPE of the
standard
winter gasoline A95 is 90.0 kPa.
A95 : GC : Ethanol: Isoamyl alcohol : Isobutanol : Naphtha : Alkylate = 55
10 : 9.2 : 0.6 : 0.2 : 12.5 : 12.5 % by volume
The boiling temperature for the naphtha is 100-200 C.
The boiling temperature for the alkylate is 100-130 C.
DVPE=89.5kPa
0.5(RON + MON) = 92.4
A95 : GC : Ethanol: Isoamyl alcohol : Naphtha : Tert-butylxylene = 55 : 10
9.5 : 0.5 : 20 : 5% by volume
The boiling temperature for the naphtha is 100-200 C.
DVPE = 89.8 kPa
0.5(RON + MON) = 92.5
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A95 : GC : Ethanol: Isobutanol : Naphtha : Isopropylbenzene = 55 : 10 : 5 : 5
: 20 : 5 % by volume
The boiling temperature for the naphtha is 100-200 C.
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 vol-
ume of gas condensate (GC), 5% by volume of ethanol, 5% by volume of tert-
butanol, 20% by volume of naphtha with boiling temperature of 100-200 C and 5%
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 require-
ments of the standards. At the same time this ethanol-containing gasoline de-
creases the level of toxic emissions in the exhaust and decreases the fuel
consump-
tion 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 698.6 kg /m3;
initial boiling point, according to
ASTM D 86 20.5 C;
vaporisable portion - 70 C 47.0 % by volume;
vaporisable portion - 100 C 65.2 % by volume;
vaporisable portion - 150 C 92.4 % by volume;
vaporisable portion - 180 C 97.3 % by volume;
final boiling point 189.9 C;
evaporation residue 0.5 % by volume;
loss by evaporation 1.1 % by volume;
oxygen content, according to ASTM
D4815 3.2% w/w;
acidity, according to ASTM D 1613
weight% HAc 0.001;
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72
pH, according to ASTM D 1287 7.0;
sulfur content, according to ASTM D 5453 18 mg/kg;
gum content, according to ASTM D381 2 mg/ 100ml;
water content, according to ASTM D6304 0.01% w/w;
aromatics, according to SS 155120,
including benzene 30.9 % by volume;
benzene alone, according to EN 238 0.7 % by volume;
DVPE, according to ASTM D 5191 90.0 kPa;
anti-knock index 0. 5 (RON+MON), according
to ASTM D 2699-86 and ASTM D 2700-86 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 -14.0%
HC -8.6%;
NOx unchanged;
CO2 + 1.0%;
NMHC -6.7%;
Fuel consumption, Fc, 1/ 100km +2.0%
Similar results are obtained when other oxygen-containing additives of the
inven-
tion 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
composi-
tion, the hydrocarbon component (HCC), which is a mixture of winter gasoline
and
gas condensate (GC), 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 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 inventive fuel formulations demonstrated the possibility of adjusting the
vapour
pressure of the ethanol-ccontaining motor fuels for the standard internal
combus-
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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
ethanol-
containing 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 85
% by volume of A92 or A95 winter gasoline.
Similar results were obtained when other oxygen-containing compounds and C6-
Ci2
hydrocarbons of this invention were used in the proportion of the invention to
for-
mulate the additive mixture, which was then used for preparation of the
ethanol-
containing 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
amo-
unt 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 5
Example 5 demonstrates the possibility of reducing the dry vapour pressure
equivalent of the ethanol-containing motor fuel for the cases when the
hydrocarbon
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74
base of the fuel is a reformulated gasoline with dry vapour pressure
equivalent ac-
cording 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
pur-
chased 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
15
% by volume of gas condensate hydrocarbon liquid (GC).
The source gasolines comprised aliphatic and alicyclic C6-C12 hydrocarbons, in-
cluding 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
in-
duces 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 0.5(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 volume
DVPE = 36.5 kPa
0.5(RON + MON) = 89.0
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A92 : PB : Ethanol= 72: 18: 10 % by volume
DVPE = 36.0 kPa
0.5(RON + MON) = 90.7
5
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
various compositions:
10 A92 : PB : Ethanol : Isoamyl alcohol = 64: 16: 10: 10 % by volume
DVPE = 27.0 kPa
0.5(RON + MON) = 90.5
A92 : PB : Ethanol : Diisobutyl ether = 64: 16 : 10 : 10 % by volume
15 DVPE = 27.5 kPa
0.5(RON + MON) = 90.8
A92 : PB : Ethanol : n-Butanol = 64: 16: 10: 10 % by volume
DVPE = 27.5 kPa
20 0.5(RON + MON) = 90.1
A92 : PB : Ethanol : 2,4,4-Trimethyl-l-pentanol = 64 : 16 : 10 : 10 % by vol-
ume
DVPE = 25.0 kPa
25 0.5(RON + MON) = 91.8
The fuel 5-3 contained reformulated A92 gasoline, Petroleum benzine (PB),
ethanol,
the oxygen-containing additives and also C8-C12 hydrocarbons and had the
follow-
ing 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
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76
0.5(RON + MON) = 89.3
A92 : PB : Ethanol : n-Butanol : Naphtha : Xylene = 60 : 15 : 9.2 : 0.8 : 7.5
:
7.5 % by volume
The boiling temperature for the naphtha is 140-200 C.
DVPE = 27.5 kPa
0.5(RON + MON) = 91.2
A92 : PB : Ethanol : Tetrahydrofurfuryl alcohol : Isopropylbenzene = 60 : 15
9: 1 15 % by volume
DVPE=27.5kPa
0.5(RON + 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 Petroleum 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
0.5(RON + MON) = 91.0
A98 : PB : Ethanol = 72: 18: 10 % by volume
DVPE = 35.8 kPa
0.5(RON + MON) = 92.5
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77
The fuel 5-5 of the invention contained A98 reformulated gasoline, Petroleum
benzine (PB), ethanol and the oxygen-containing additives and had the
following
properties for the various compositions:
A98 : PB : Ethanol : Isoamyl alcohol = 64 :16 : 10: 10 % by volume
DVPE = 26.9 kPa
0.5(RON + MON) = 92.0
A98 : PB : Ethanol : n-Amyl alcohol = 64 :16 : 10: 10 % by volume
DVPE = 26.5 kPa
0.5(RON + 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-Dimethyl-3-octanol = 68 :17 : 9: 6 /o by volume
DVPE = 27.0 kPa
0.5(RON + MON) = 92.5
The fuel 5-6 contained A98 reformulated gasoline, Petroleum benzine (PB),
ethanol,
the oxygen-containing additives, and Cs-C12 hydrocarbons (d) 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
0.5(RON + MON) = 91.7
A98 : PB : Ethanol : Linalool : Allocymene = 60: 15 : 9 : 1: 15 % by volume
DVPE = 26.0 kPa
0.5(RON + MON) = 93.0
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A98 : PB : Ethanol : Methylcyclohexanol : Limonene = 60: 15 : 9.5: 1: 14.5
% by volume
DVPE=25.4kPa
0.5(RON + 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
80 % by volume of reformulated A95 gasoline and about 20 % by volume of the
Pet-
roleum benzine (PB). Gasoline comprising 80 % by volume of the reformulated
A95
gasoline and 20 % by volume of the Petroleum benzine (PB) had the following
pro-
perties:
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:
A95 : PB : Ethanol = 76: 19 : 5% by volume
DVPE = 36.6 kPa
0.5(RON + MON) = 90.2
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79
A95 : PB : Ethanol = 72: 18: 10 % by volume
DVPE = 36.1 kPa
0.5(RON + MON) = 91.7
The reference fuel mixture (RFM5) comprising 72 % by volume of reformulated
A95
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
vol-
ume of Petroleum benzine (GC) :
CO -4.8%
HC -1.3%;
NOx +26.3%;
C02 +4.4%;
NMHC -0.6%;
Fuel consumption, Fc, 1/ 100km +5.7%.
The fuel 5-8 contained A95 reformulated gasoline, Petroleum benzine (PB),
ethanol
and the oxygen-containing additives and had the following properties for the
vari-
ous compositions:
A95 : PB : Ethanol : Isoamyl alcohol = 64: 16: 10: 10 % by volume
DVPE = 27.1 kPa
0.5(RON + MON) = 92.0
A95 : PB : Ethanol : 2,6-Dimethyl-4-heptanol = 64 : 16 : 10 : 10 % by vol-
ume
DVPE = 27.0 kPa
0.5(RON + MON) = 92.4
A95 : PB : Ethanol : Tetrahydrofurfuryl acetate = 60 : 15 : 15 : 10 % by vol-
ume
DVPE = 25.6 kPa
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0.5(RON + MON) = 93.0
The fuel 5-9 contained A95 reformulated gasoline, Petroleum benzine (PB),
ethanol,
the oxygen-containing additives, and C8-C12 hydrocarbons and had the following
5 properties for the various compositions:
A95 : PB : Ethanol: Isoamyl alcohol : Naphtha = 60 : 15 : 9.2 : 0.8 : 15 % by
volume
The boiling temperature for the naphtha is 140-200 C.
10 DVPE = 27.1 kPa
0.5(RON + MON) = 91.4
A95 : PB : Ethanol: Tetrahydrofurfuryl alcohol : Tert-butylcyclohexane = 60 :
15 : 9.2 : 0.8 : 15 % by volume
15 DVPE = 26.5 kPa
0.5(RON + MON) = 90.7
A95 : PB : Ethanol: 4-Methyl-4-hydroxytetrahydropyran : Isopropyltoluene =
60: 15 : 9.2 : 0.8 : 15 % by volume
20 DVPE = 26.1 kPa
0.5(RON + MON) = 92.0
The motor fuel 5-10 contained 60% by volume of A95 reformulated gasoline, 15%
by volume of Petroleum benzine (PB), 10% by volume of ethanol, 5% by volume of
25 2,5-Dimethyltetrahydrofuran and 10% by volume of isopropyltoluene.
Formulation
5-10 was tested to demonstrate how the invention enables the formulation of
etha-
nol-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
pres-
sure equivalent in comparison to the source hydrocarbon component (HCC). Moreo-
30 ver, this gasoline secures a decrease of toxic emissions in the exhaust and
a de-
crease 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
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81
D4052 764.6 kg /m3;
initial boiling point, according to
ASTM D 86 48.9 C;
vaporisable portion - 70 C 25.3 % by volume;
vaporisable portion - 100 C 50.8 % by volume;
vaporisable portion - 150 C 76.5 % by volume;
vaporisable portion - 190 C 95.6 % by volume;
final boiling point 204.5 C;
evaporation residue 1.4 % by volume;
loss by evaporation 0.5 % by volume;
oxygen content, according to ASTM
D4815 4.6% w/w;
acidity, according to ASTM D 1613
weight% HAc 0.08;
pH, according to ASTM D1287 7.5;
sulfur content, according to ASTM D 5453 39 mg/kg;
gum content, according to ASTM D381 1.5 mg/ 100m1;
water content, according to ASTM D6304 0.1% w/w;
aromatics, according to SS 155120,
including benzene 38 % by volume;
benzene alone, according to EN 238 0.4 % by volume;
DVPE, according to ASTM D 5191 27.2 kPa;
anti-knock index 0.5(RON+MON), according
to ASTM D 2699-86 and ASTM D 2700-86 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 com-
prising 80 % by volume of reformulated A95 gasoline and 20 % by volume of
Petro-
leum benzine:
CO -12.3%
HC -6.2%;
NOx unchanged;
C02 +2.6%;
NMHC -6.4%;
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82
Fuel consumption, Fc, 1/ 100km +3.7%
Similar results are obtained when other oxygen-containing additives of the
inven-
tion 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
composi-
tion, 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 C8-C12
hydrocarbons.
The motor fuel composition obtained was then allowed to stand before testing
be-
tween 1 and 24 hours at a temperature not lower than -35 C. All the above
formu-
lations 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 reformu-
lated A92 gasoline and 20 % by volume of Petroleum benzine, with the oxygen-
containing additive mixture 5, comprising 40 % by volume of ethanol, 20 % by
vo-
lume 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 de-
monstrates that the use of the additive of this invention enables obtaining
ethanol-
containing 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 oxygen-
containing 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 Cs-
C12
hydrocarbons of this invention were used in the proportion of the invention to
for-
CA 02397579 2002-07-15
WO 01/53437 PCT/SE01/00040
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 anti-
knock 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.
