U.S. patent application number 09/767940 was filed with the patent office on 2001-11-01 for method of reducing the vapor pressure of ethanol-containing motor fuels for spark ignition combustion engines.
Invention is credited to Golubkov, Angelica, Golubkov, Igor.
Application Number | 20010034966 09/767940 |
Document ID | / |
Family ID | 24453739 |
Filed Date | 2001-11-01 |
United States Patent
Application |
20010034966 |
Kind Code |
A1 |
Golubkov, Angelica ; et
al. |
November 1, 2001 |
Method of reducing the vapor pressure of ethanol-containing motor
fuels for spark ignition combustion engines
Abstract
Method of reducing the pressure of a C.sub.3 to C.sub.12
hydrocarbon-based motor fuel mixture containing 0.1 to 20% by
volume of ethanol for conventional spark ignition internal
combustion engines, wherein, in addition to an ethanol component
(b) and a C.sub.3 to C.sub.12 hydrocarbon component (a), an
oxygen-containing additive (c) selected from at least one of the
following types of compounds: alcohol other than ethanol, ketone,
ether, ester, hydroxy ketone, ketone ester, and a
heterocyclic-containing oxygen compound, is used in the fuel
mixture in an amount of at least 0.05 by volume of the total fuel,
is disclosed. A mixture of fuel grade ethanol (b) and
oxygen-containing additive (c) usable in the method of the
invention is also disclosed.
Inventors: |
Golubkov, Angelica;
(Lidingo, SE) ; Golubkov, Igor; (Lidingo,
SE) |
Correspondence
Address: |
FITZPATRICK CELLA HARPER & SCINTO
30 ROCKEFELLER PLAZA
NEW YORK
NY
10112
US
|
Family ID: |
24453739 |
Appl. No.: |
09/767940 |
Filed: |
January 24, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09767940 |
Jan 24, 2001 |
|
|
|
09612572 |
Jul 7, 2000 |
|
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Current U.S.
Class: |
44/329 ; 44/350;
44/437; 44/447; 44/451 |
Current CPC
Class: |
C10L 10/10 20130101;
C10L 10/02 20130101 |
Class at
Publication: |
44/329 ; 44/350;
44/437; 44/447; 44/451 |
International
Class: |
C10L 001/18; C10L
001/24 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 24, 2000 |
SE |
PCT/SE00/00139 |
Claims
What is claimed is:
1. A method for providing a hydrocarbon-based motor fuel
composition for conventional spark ignition internal combustion
engines having a reduced vapor pressure comprising combining: (a) a
hydrocarbon component comprising C.sub.3 to C.sub.12 hydrocarbon
fractions; (b) an ethanol component comprising fuel grade ethanol
for conventional spark ignition internal combustion engines, said
ethanol component comprising 0.1% to 20% of the composition by
volume; and (c) an oxygen-containing additive comprising at least
one compound selected from the group consisting of alcohol other
than ethanol, ketone, ether, ester, hydroxyketone, ketone ester and
a heterocyclic compound containing oxygen, said oxygen-containing
additive comprising at least 0.05% of the composition by
volume.
2. The method according to claim 1, wherein the oxygen-containing
additive (c) is added to the ethanol component (b) and then a
mixture of (b) and (c) is added to the hydrocarbon component
(a).
3. The method according to claim 1, wherein the ethanol component
(b) is added to the hydrocarbon component (a) and then the
oxygen-containing additive (c) is combined with a mixture of (b)
and (a).
4. A method according to any one of claims 1-3, wherein the
oxygen-containing additive (c) is at least one compound selected
from the group consisting of (1) an alkanol having from 3 to 10
carbon atoms; (2) a ketone having from 4 to 9 carbon atoms; (3) a
dialkyl ether having from 6 to 10 carbon atoms; (4) an alkyl ester
of an alkanoic acid, said alkyl ester having 5 to 8 carbon atoms;
(5) a hydroxyketone having 4 to 6 carbon atoms; (6) a ketone ester
of an alkanoic acid, said ketone ester having 5 to 8 carbon atoms;
and (7) an oxygen-containing heterocyclic compound having 5 to 8
carbon atoms.
5. A method according to any one of claims 1-3, wherein the
hydrocarbon component (a) is a non-reformulated standard gasoline,
a hydrocarbon liquid from petroleum refining, a hydrocarbon liquid
from natural gas, a hydrocarbon liquid from an off-gas of
chemical-recovery carbonization, a hydrocarbon liquid from
synthesis gas processing or mixtures thereof.
6. A method according to any one of claims 1-3, wherein a denatured
ethanol mixture comprising about 92% by volume of ethanol and about
8% by volume of hydrocarbons and by-products is present in the
motor fuel composition.
7. A method according to any one of claims 1-3, wherein the ethanol
component (b) comprises at least about by volume 99.5% of
ethanol.
8. A method according to any one of claims 1-3, wherein the
components (a), (b) and (c) are combined without being mixed and
the resulting motor fuel composition is permitted to stand for at
least one hour prior to use.
9. A method according to any one of claims 1-3, wherein the
oxygen-containing additive (c) is present in amounts up to 15% by
volume of the motor fuel composition.
10. A method according to any one of claims 1-3, wherein the motor
fuel composition exhibits the following characteristics: (i) a
density at 15.degree. C., according to ASTM D-4059 of at least 690
kg /m.sup.3; (ii) an oxygen content according to ASTM D-4815 of no
greater than 7% w/w; (iii) a dry vapor pressure equivalent
according to ASTM D-5191 from 20 kPa to 120 kPa; (iv) an acids
content according to ASTM D-1613 of no greater than 0.1 weight %
HAc; (v) a pH according to ASTM D-1287 from 5 to 9; (vi) an
aromatics content according to SS 155120 of no greater than 40% by
volume, wherein benzene is present in amounts according to EN 238
no greater than 1% by volume; (vii) a sulfur content according to
ASTM D-5453 of no greater than 50 mg/kg; (viii) a gum content
according to ASTM D-381 of no greater than 2 mg/100 ml; (ix) a
water content according to ASTM D-6304 of no greater than 0.25%
w/w; (x) distillation properties according to ASTM D-86, wherein
initial boiling point is at least 20.degree. C.; a vaporizable
portion at 70.degree. C. is at least 25% by volume; a vaporizable
portion at 100.degree. C. is at least 50% by volume; a vaporizable
portion at 150.degree. C. is at least 75% by volume; a vaporizable
portion at 190.degree. C. is at least 95% by volume; a final
boiling point no greater than 205.degree. C.; and an evaporation
residue no greater than 2% by volume; and (xi) an anti-knock index
0.5 (RON+MON) according to ASTM D-2699-86 and ASTM D-2700-86 of at
least 80.
11. A method according to any one of claims 1-3, wherein vapor
pressure increase induced by the ethanol component (b) is reduced
by at least 50%.
12. The method according to claim 11, wherein vapor pressure
increase induced by the ethanol component (b) is reduced by at
least 80%.
13. The method according to claim 12, wherein vapor pressure
increase induced by the ethanol component (b) is reduced by
100%.
14. A motor fuel composition for a conventional spark ignition
internal combustion engine comprising: (a) a hydrocarbon component
comprising C.sub.3-C.sub.12 hydrocarbon fractions; (b) a fuel grade
ethanol comprising 0.1% to 20% of a total volume of the motor fuel
composition; and (c) an oxygen-containing additive comprising at
least one of (1) an alkanol having from 3 to 10 carbon atoms; (2) a
ketone having from 4 to 9 carbon atoms; (3) a dialkyl ether having
from 6 to 10 carbon atoms; (4) an alkyl ester of an alkanoic acid,
said alkyl ester having 5 to 8 carbon atoms; (5) a hydroxyketone
having 4 to 6 carbon atoms; (6) a ketone ester of an alkanoic acid,
said ketone ester having 5 to 8 carbon atoms or (7) an
oxygen-containing heterocyclic compound having 5 to 8 carbon atoms,
and said oxygen-containing additive comprises 0.05% to 15% of the
total volume of the motor fuel composition.
15. The composition according to claim 14, wherein said fuel grade
ethanol (b) comprises 1% to 20% of the total volume of the motor
fuel composition.
16. The composition according to claim 14, wherein wherein said
fuel grade ethanol (b) comprises 3% to 15% of the total volume of
the motor fuel composition.
17. The composition according to claim 14, wherein wherein said
fuel grade ethanol (b) comprises 5% to 10% of the total volume of
the motor fuel composition.
18. The composition according to claim 14, wherein said
oxygen-containing additive (c) comprises 0.1% to 15% of the total
volume of the motor fuel composition.
19. The composition according to claim 14, wherein said
oxygen-containing additive (c) comprises 3% to 10% of the total
volume of the motor fuel composition.
20. The composition according to claim 14, wherein said
oxygen-containing additive (c) comprises 5% to 10% of the total
volume of the motor fuel composition.
21. A mixture utilized in preparation of a motor fuel composition
comprising: (i) a fuel grade ethanol (b) and (ii) an
oxygen-containing additive (c) comprising at least one of (1) an
alkanol having from 3 to 10 carbon atoms; (2) a ketone having from
4 to 9 carbon atoms; (3) a dialkyl ether having from 6 to 10 carbon
atoms; (4) an alkyl ester of an alkanoic acid, said alkyl ester
having 5 to 8 carbon atoms; (5) a hydroxyketone having 4 to 6
carbon atoms; (6) a ketone ester of an alkanoic acid, said ketone
ester having 5 to 8 carbon atoms or (7) an oxygen-containing
heterocyclic compound having 5 to 8 carbon atoms, wherein a ratio
of (b) to (c) is from 1:150 to 400:1 by volume.
22. The mixture according to claim 21, wherein the ratio of (b) to
(c) is from 1:10 to 10:1 by volume.
23. A mixture utilized in preparation of a motor fuel composition
comprising: (i) a fuel grade ethanol (b) in an amount of 0.5% to
99.5% by volume; (ii) an oxygen-containing additive (c) in an
amount of 0.5% to 99.5% by volume, said oxygen-containing additive
(c) comprising at least one of (1) an alkanol having from 3 to 10
carbon atoms; (2) a ketone having from 4 to 9 carbon atoms; (3) a
dialkyl ether having from 6 to 10 carbon atoms; (4) an alkyl ester
of an alkanoic acid, said alkyl ester having 5 to 8 carbon atoms;
(5) a hydroxyketone having 4 to 6 carbon atoms; (6) a ketone ester
of an alkanoic acid, said ketone ester having 5 to 8 carbon atoms
or (7) an oxygen-containing heterocyclic compound having 5 to 8
carbon atoms; and (iii) at least one C.sub.5-C.sub.12 hydrocarbon
as a component (d) in an amount of up to 99% by volume, wherein the
ratio between the components in the mixture (b)/{(c)+(d)} is from
1:200 up to 200:1.
24. The mixture according to claim 23, wherein said component (d)
is at least one C.sub.8-C.sub.11 hydrocarbon.
25. The mixture according to claim 23, including up to 90% by
volume of said component (d).
26. The mixture according to claim 23, including up to 79.5% by
volume of said component (d).
27. The mixture according to claim 23, comprising from 5% to 77% by
volume of said component (d).
28. The mixture according to claim 23, comprising 9.5% to 99% by
volume of said component (b).
29. The mixture according to claim 23, comprising 20% to 95% by
volume of said component (b).
30. The mixture according to claim 23, comprising 25% to 92% by
volume of said component (b).
31. The mixture according to claim 23, comprising 0.5% to 90% by
volume of said component (c).
32. The mixture according to claim 23, comprising 0.5% to 80% by
volume of said component (c).
33. The mixture according to claim 23, comprising 3% to 70% by
volume of said component (c).
34. The mixture according to claim 23, wherein the ratio between
the components in the mixture (b)/{(c)+(d)} is from 1:10 up to
10:1.
35. The mixture of claim 23, wherein said component (d) is at least
one of a saturated aliphatic hydrocarbon, unsaturated aliphatic
hydrocarbon, alicyclic saturated hydrocarbon, alicyclic unsaturated
hydrocarbon, or a fraction of hydrocarbons boiling at
100-200.degree. C., said fraction of hydrocarbons obtained in
distillation of oil, bituminous coal resin or products yielded from
processing of synthesis-gas.
36. The mixture according to claim 21, wherein a denatured ethanol
mixture comprising about 92% by volume of ethanol and about 8% by
volume of hydrocarbons and by-products is present.
37. The mixture according to claim 21, wherein said fuel grade
ethanol (b) comprises at least about 99.5% by volume of
ethanol.
38. The mixture according to claim 23, wherein a denatured ethanol
mixture comprising about 92% by volume of ethanol and about 8% by
volume of hydrocarbons and by-products is present.
39. The mixture according to claim 23, wherein said fuel grade
ethanol (b) comprises at least about 99.5% by volume of
ethanol.
40. A method of making a fuel for use in a conventional spark
ignition internal combustion engine comprising combining a
sufficient amount of the mixture according to any one of claims
21-39 with a conventional gasoline fuel to provide a vapor pressure
of the combination that is no greater than the vapor pressure of
the conventional gasoline fuel.
41. A fuel for use in a conventional spark ignition internal
combustion engine made according to the method of claim 40.
42. The fuel according to claim 41, wherein an octane number of the
combination is at least the same as that of the conventional
gasoline fuel.
43. The fuel according to claim 41, wherein an octane number of the
combination meets mandatory regulation limits for octane
numbers.
44. A fuel for use in a modified gasoline engine comprising: (i) a
fuel grade ethanol (b) and (ii) an oxygen-containing additive (c)
comprising at least one of (1) an alkanol having from 3 to 10
carbon atoms; (2) a ketone having from 4 to 9 carbon atoms; (3) a
dialkyl ether having from 6 to 10 carbon atoms; (4) an alkyl ester
of an alkanoic acid, said alkyl ester having 5 to 8 carbon atoms;
(5) a hydroxyketone having 4 to 6 carbon atoms; (6) a ketone ester
of an alkanoic acid, said ketone ester having 5 to 8 carbon atoms
or (7) an oxygen-containing heterocyclic compound having 5 to 8
carbon atoms, wherein a ratio of (b) to (c) is from 1:150 to 400:1
by volume.
45. A fuel for use in a modified gasoline engine comprising: (i) a
fuel grade ethanol (b) in an amount of 0.5% to 99.5% by volume;
(ii) an oxygen-containing additive (c) in an amount of 0.5% to
99.5% by volume, said oxygen-containing additive (c) comprising at
least one of (1) an alkanol having from 3 to 10 carbon atoms; (2) a
ketone having from 4 to 9 carbon atoms; (3) a dialkyl ether having
from 6 to 10 carbon atoms; (4) an alkyl ester of an alkanoic acid,
said alkyl ester having 5 to 8 carbon atoms; (5) a hydroxyketone
having 4 to 6 carbon atoms; (6) a ketone ester of an alkanoic acid,
said ketone ester having 5 to 8 carbon atoms or (7) an
oxygen-containing heterocyclic compound having 5 to 8 carbon atoms;
and (iii) at least one C.sub.5-C.sub.12 hydrocarbon as a component
(d) in an amount of up to 99% by volume, wherein the ratio between
the components in the mixture (b)/{(c)+(d)} is from 1:200 up to
200:1.
Description
[0001] This application is a continuation-in-part of application
Ser. No. 09/612,572, filed on Jul. 7, 2000.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to motor fuel for spark ignition
internal combustion engines. More particularly the invention
relates to a method for lowering the dry vapor pressure equivalent
(DVPE) of a fuel composition including a hydrocarbon liquid and
ethanol by using an oxygen-containing additive. The ethanol and
DVPE adjusting components used to obtain the fuel composition are
preferably derived from renewable raw materials. By means of the
method of the invention motor fuels containing up to 20% by volume
of ethanol meeting standard requirements for spark ignition
internal combustion engines operating with gasoline are
obtainable.
[0004] 2. Background of the Invention
[0005] Conventional gasoline ("gasoline") is the major fuel for
spark ignition internal combustion engines. As employed herein, the
phrase "conventional gasoline" includes a volatile, highly
inflammable, generally colorless, liquid obtained by fractional
distillation of petroleum. The extensive use of gasoline results in
the pollution of the environment. The combustion of gasoline
derived from crude oil or mineral gas disturbs the carbon dioxide
balance in the atmosphere, and causes the greenhouse effect. Crude
oil reserves are decreasing steadily with some countries already
facing crude oil shortages.
[0006] 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.
[0007] The existing global inventory of vehicles and machinery
operating with spark ignition internal combustion engines does not
allow currently the complete elimination of gasoline as a motor
fuel.
[0008] The task of creating alternative fuels for internal
combustion engines has existed for a long time and a large number
of attempts have been made to use renewable resources for yielding
motor fuel components.
[0009] U.S. Pat. No. 2,365,009, issued in 1944 describes the
combination of C.sub.1-5 alcohols and C.sub.3-5 hydrocarbons for
use as a fuel. In U.S. Pat. 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. Pat.
No. 5,607,486 issued in 1997, there are disclosed novel engine fuel
additives comprising terpenes, aliphatic hydrocarbons and lower
alcohols.
[0010] Currently tert-butyl ethers are widely used as components of
gasolines. Motor fuels comprising tert-butyl ethers are described
in U.S. Pat. No. 4,468,233 issued in 1984. The major portion of
these ethers is obtained from petroleum refining, but can equally
be produced from renewable resources.
[0011] 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.
[0012] The combustion of ethanol produces significantly less
harmful substances in comparison to the combustion of gasoline.
However, the use of a motor fuel principally containing ethanol
requires specially designed engines. At the same time spark
ignition internal combustion engines normally operating on gasoline
can be operated with a motor fuel comprising a mixture of gasoline
and not more than about 10% by volume of ethanol. Such a mixture of
gasoline and ethanol is presently sold in the United States as
gasohol. Current European regulations concerning gasolines allow
the addition to gasoline of up to 5% by volume of ethanol.
[0013] The major disadvantage of mixtures of ethanol and
conventional gasoline is that for mixtures containing up to about
20% by volume of ethanol there is an increase in the dry vapor
pressure equivalent as compared to that of the conventional
gasoline.
[0014] FIG. 1 shows the behavior of the dry vapor 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.degree. C. The gasolines known as A92 and A95 are
standard, conventional 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 D-5191 method at the
SGS laboratory in Stockholm, Sweden.
[0015] For the range of concentrations by volume of ethanol between
5 and 10% which is of particular interest for use as a motor fuel
for standard spark ignition engines, the data in FIG. 1 show that
the DVPE of mixtures of gasoline and ethanol can exceed the DVPE of
source gasoline by more than 10%. Since the commercial petroleum
companies normally supply the market with gasoline already at the
maximum allowed DVPE, which is strictly limited by current
regulations, the addition of ethanol to such presently commercially
available gasolines is not possible.
[0016] It is known that the DVPE of mixtures of gasoline and
ethanol can be adjusted. U.S. Pat. No. 5,015,356 granted on May 14,
1991 proposes reformulating gasoline by removing both the volatile
and non-volatile components from C.sub.4-C.sub.12 gasoline to yield
either C.sub.6-C.sub.9 or C.sub.6-C.sub.10 intermediate gasoline.
Such fuels are said to better facilitate the addition of alcohol
over current gasoline because of their lower dry vapor pressure
equivalent (DVPE). A disadvantage of this method of adjusting the
DVPE of mixtures of gasoline and ethanol is that in order to obtain
such a mixture it is necessary to produce a special reformulated
gasoline, which adversely affects the supply chain and results in
increased prices for the motor fuel. Also, such gasolines and their
mixtures with ethanol have a higher flash point, which impairs
their performance properties.
[0017] It is known that some chemical components decrease DVPE when
added to gasoline or to a mixture thereof with ethanol. For
example, U.S. Pat. No. 5,433,756 granted on Jul. 18, 1995 discloses
chemical clean-combustion-promoter compounds comprising, in
addition to gasoline, ketones, nitro-paraffin and also alcohols
other than ethanol. It is noted that the composition of the
catalytic clean-combustion-promoter disclosed in the patent reduces
the DVPE of gasoline fuel. Nothing is mentioned in this patent
about the impact of the clean-combustion-promoter composition on
the DVPE of mixtures of gasoline and ethanol.
[0018] U.S. Pat. No. 5,688,295 granted on Nov. 18, 1997 provides a
chemical compound as an additive to gasoline or as a fuel for
standard gasoline engines. In accordance with the invention, an
alcohol-based fuel additive is proposed. The fuel additive
comprises from 20-70% alcohol, from 2.5-20% ketone and ether, from
0.03-20% aliphatic and silicon compounds, from 5-20% toluene and
from 4-45% 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 combustion, results in increased engine wear.
[0019] In WO9743356 a method for lowering the vapor pressure of a
hydrocarbon-alcohol blend by adding a co-solvent for the
hydrocarbon and alcohol to the blend, is described. A spark
ignition motor fuel composition is also disclosed, including a
hydrocarbon component of C.sub.5-C.sub.8 straight-chained or
branched alkanes, essentially free of olefins, aromatics, benzene
and sulphur, in which the hydrocarbon component has a minimum
anti-knock index of 65, according to ASTM D-2699 and D-2700 and a
maximum DVPE of 15 psi, according to ASTM D-5191; a fuel grade
alcohol; and a co-solvent for the hydrocarbon component and alcohol
in which the components of the fuel composition are present in
amounts selected to provide a motor fuel with a minimum anti-knock
index of 87 and a maximum DVPE of 15 psi. The co-solvent used is
biomass-derived 2-methyltetrahydrofuran (MTHF) and other
heterocyclical ethers such as pyrans and oxepans, MTHF being
preferred.
[0020] The disadvantages of this method for adjusting the dry vapor
pressure equivalent of mixtures of hydrocarbon liquid and ethanol
are the following:
[0021] (1) It is necessary to use only hydrocarbon components
C.sub.5-C.sub.8 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
description of the invention, (iii) the hydrocarbon component is a
coal gas condensate or natural gas condensate;
[0022] (2) It is necessary to use as a co-solvent for the
hydrocarbon component and ethanol only one particular class of
chemical compounds containing oxygen; namely, ethers, including
short-chained and heterocyclic ethers;
[0023] (3) It is necessary to use a large quantity of ethanol in
the fuel, not less than 25%;
[0024] (4) It is necessary to use a large quantity of co-solvent,
not less than 20%, of 2-methyltetrahydrofuran; and
[0025] (5) It is required to modify the spark ignition internal
combustion engine when operating with such fuel composition and,
specifically, one must change the software of the on-board computer
or replace the on-board computer itself.
[0026] 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 vapor pressure of a C.sub.3 to
C.sub.12 hydrocarbon based fuel mixture containing up to 20% by
volume of ethanol for conventional gasoline engines to not more
than the vapor pressure of the C.sub.3 to C.sub.12 hydrocarbon
itself, or at least so as to meet the standard requirement on
gasoline fuel.
SUMMARY OF THE INVENTION
[0027] The above-mentioned object of the present invention has been
accomplished by means of the method comprising combining:
[0028] (a) a hydrocarbon component comprising C.sub.3 to C.sub.12
hydrocarbon fractions;
[0029] (b) an ethanol component comprising fuel grade ethanol for
conventional spark ignition internal combustion engines, said
ethanol component comprising 0.1% to 20% of the composition by
volume; and
[0030] (c) an oxygen-containing additive comprising at least one
compound selected from the group consisting of alcohol other than
ethanol, ketone, ether, ester, hydroxyketone, ketone ester and a
heterocyclic compound containing oxygen, said oxygen-containing
additive comprising at least 0.05% of the composition by
volume.
[0031] The present inventors have found that specific types of
compounds exhibiting an oxygen-containing group surprisingly lowers
the vapor pressure of a gasoline-ethanol mixture.
[0032] This effect can unexpectedly be further enhanced by means of
specific C.sub.6-C.sub.12 hydrocarbon compounds.
[0033] They have also found that the octane number of the resulting
hydrocarbon based fuel mixture can surprisingly be maintained or
even increased by using the oxygen-component of the present
invention.
[0034] According to the present method, up to about 20% by volume
of fuel grade ethanol (b) can be used in the overall fuel
compositions. The oxygen-containing additives (c) used can be
obtained from renewable raw materials, and the hydrocarbon
component (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.
[0035] 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.
[0036] According to one aspect of the invention, in addition to the
dry vapor pressure equivalent (DVPE), the anti-knock index (octane
number) can also be desirably controlled. The octane number can be
at least the same as that of the hydrocarbon component (a) or meet
mandatory regulation limits for octane numbers.
[0037] It is yet another object to provide an additive mixture of
fuel grade ethanol (b) and oxygen-containing additive (c), and
optionally, an additional component (d), wherein component (d)
comprises at least one C.sub.6-C.sub.12 hydrocarbon and is present
in an amount up to 99% by volume. This mixture can then be
subsequently can be used in the method of the present invention,
i.e., added to the hydrocarbon component (a).
[0038] 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 additive mixture can also be used for
adjusting the octane number and/or for lowering the vapor pressure
of a high vapor pressure hydrocarbon component.
[0039] 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
[0040] In FIG. 1, the behavior of the dry vapor pressure equivalent
(DVPE) as a function of the ethanol content of prior art mixtures
of ethanol and gasoline is shown.
[0041] In FIG. 2, the behavior of the dry vapor 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
[0042] The present method enables the use of C.sub.3-C.sub.12
hydrocarbon fractions as hydrocarbon 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 carbonization, natural gas and
synthesis gas.
[0043] Hydrocarbons obtained from renewable raw materials can also
be included. The C.sub.3-C.sub.12 fractions are usually prepared by
fractional distillation or by blending various hydrocarbons.
[0044] 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.
[0045] According to the method of the present invention the DVPE
can be reduced for fuel mixtures containing up to 20% by volume of
ethanol, calculated as pure ethanol. According to a preferred
embodiment the vapor pressure of the hydrocarbon based
ethanol-containing fuel mixture is reduced by 50% of the
ethanol-induced vapor pressure increase, more preferably by 80%,
and even more preferably the vapor pressure of the hydrocarbon
based ethanol-containing fuel mixture is reduced by 100%, which
leads to a vapor pressure corresponding to that of the hydrocarbon
component alone, and/or to the vapor pressure according to any
standard requirement on commercially sold gasoline.
[0046] As will be evident from the examples, the DVPE can, if
desired, be reduced to a level even lower than that of the
hydrocarbon component used.
[0047] According to the most preferred embodiment, the other
properties of the fuel, such as for example the octane number, are
kept within the required standard limits.
[0048] This is accomplished by combining:
[0049] (a) a hydrocarbon component comprising C.sub.3 to C.sub.12
hydrocarbon fractions;
[0050] (b) an ethanol component comprising fuel grade ethanol for
conventional spark ignition internal combustion engines, said
ethanol component comprising 0.1% to 20% of the composition by
volume; and
[0051] (c) an oxygen-containing additive comprising at least one
compound selected from the group consisting of alcohol other than
ethanol, ketone, ether, ester, hydroxyketone, ketone ester and a
heterocyclic compound containing oxygen, said oxygen-containing
additive comprising at least 0.05% of the composition by
volume.
[0052] The oxygen-containing organic compound enables the
adjustment of (i) the dry vapor pressure equivalent, (ii) the
anti-knock index and other performance parameters of the motor fuel
composition as well as (iii) the reduction of the fuel consumption
and the reduction of toxic substances in the engine exhaust
emissions. The oxygen-containing compound (c) has oxygen bound in
at least any one of the following functional groups: 1
[0053] 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,
hydroxyketones, ketone esters, and with oxygen-containing
heterocyclic rings.
[0054] The fuel additive can be derived from fossil-based sources
or preferably from renewable sources such as biomass.
[0055] The oxygen-containing fuel additive (c) can typically be an
alcohol, other than ethanol. In general, aliphatic or alicyclic
alcohols, both saturated and unsaturated, preferably alkanols, are
employed. More preferably, alkanols of the general formula: R--OH
where R is an alkyl group 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,
diisopropylcarbinol, 2-ethylhexanol, 2,4,4-trimethylpentanol,
2,6-dimethyl-4-heptanol, linalool, 3,6-dimethyl-3-octanol, phenol,
phenylmethanol, methylphenol, methylcyclohexanol or similar
alcohols, are employed, as well as their mixtures.
[0056] The component (c) can also be an aliphatic or alicyclic
ketone, both saturated and unsaturated, of the general formula
R--C--R', where R and R' are the same or different and are each
C.sub.1-C.sub.6 hydrocarbons, which also can be cyclic, and are
preferably C.sub.1-C.sub.4 hydrocarbons. Preferred ketones have a
total (R+R') of 4 to 9 carbon atoms and include methylethyl ketone,
methylpropyl ketone, diethylketone, methylisobutyl ketone,
3-heptanone, 2-octanone, diisobutyl ketone, cyclohexanone,
acetofenone, trimethylcyclohexanone, or similar ketones, and
mixtures thereof.
[0057] The component (c) can also be an aliphatic or alicyclic
ether, including both saturated and unsaturated ethers, of the
general formula R--O--R', wherein R and R' are the same or
different and are each a C.sub.1-C.sub.10 hydrocarbon group. In
general, lower (C.sub.1-C.sub.6) dialkyl ethers are preferred. The
total number of carbon atoms in the ether is preferably from 6 to
10. Typical ethers include methyl-tert-amyl ether, methylisoamyl
ether, ethylisobutyl ether, ethyl-tert-butyl ether, dibutyl ether,
diisobutyl ether, diisoamyl ether, anisole, methylanisole,
phenetole or similar ethers and mixtures thereof.
[0058] The component (c) may further be an aliphatic or alicyclic
ester, including saturated and unsaturated esters, of the general
formula 2
[0059] where R and R' are the same or different. R and R' are
preferably hydrocarbon groups, more preferably alkyl groups and
most preferably alkyl and phenyl having 1 to 6 carbon atoms.
Especially preferred is an ester where R is C.sub.1-C.sub.4 and R'
is C.sub.4-C.sub.6. Typical esters are alkyl esters of alkanoic
acids, including n-butylacetate, isobutylacetate,
tert-butylacetate, isobutylpropionate, isobutylisobutyrate,
n-amylacetate, isoamylacetate, isoamylpropionate, methylbenzoate,
phenylacetate, cyclohexylacetate, or similar esters and mixtures
thereof. In general, it is preferred to employ an ester having from
5 to 8 carbon atoms.
[0060] The additive (c) can simultaneously contain two
oxygen-containing groups connected in the same molecule with
different carbon atoms.
[0061] The additive (c) can be a hydroxyketone. A preferred
hydroxyketone has the general formula: 3
[0062] wherein R is an alkyl group, and R.sub.1 is hydrogen or an
alkyl group, preferably a lower alkyl group, i.e.
(C.sub.1-C.sub.4). In general, it is preferred to employ a ketol
having 4 to 6 carbon atoms. Typical hydroxyketones include
1-hydroxy-2-butanone, 3-hydroxy-2-butanone,
4-hydroxy-4-methyl-2-pentanone, or similar ketols or mixture
thereof.
[0063] In yet another embodiment the fuel additive (c) is a ketone
ester, preferably of the general formula: 4
[0064] where R is an alkyl group, preferably a lower alkyl group,
i.e. (C.sub.1-C.sub.4).
[0065] Typical ketone esters include methylacetoacetate, ethyl
acetoacetate and tert-butyl acetoacetate. Preferably, such ketone
esters have 6 to 8 carbon atoms, and, more preferably, 5 to 8
carbon atoms.
[0066] The additive (c) can also be a ring-oxygen-containing
heterocyclic compound and, preferably, the oxygen-containing
heterocycle has a C.sub.4-C.sub.5 ring. More preferably, the
heterocycle additive has a total of 5 to 8 carbon atoms. The
additive can preferably have the formula (1) or (2) as follows:
5
[0067] wherein R is hydrogen or an alkyl group, preferably
--CH.sub.3, and R.sub.1 is --CH.sub.3, or --OH, or --CH.sub.2OH, or
CH.sub.3CO.sub.2CH.sub.2--.
[0068] A typical heterocyclic additive (c) is tetrahydrofurfuryl
alcohol, tetrahydrofurfuryl acetate, dimethyltetrahydrofuran,
tetramethyltetrahydrofuran, methyltetrahydropyran,
4-methyl-4-oxytetrahydropyran or similar heterocyclic additives, or
mixtures thereof.
[0069] 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.
[0070] 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 ethanol component is an
ethanol component comprising at least about 99.5% ethanol by
volume. 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 account when
determining the amount used of component (c). That is, such
impurities must be included in an amount of at least 0.5% in the
ethanol in order to be taken into account as a part of component
(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 for gasoline engine
fuels.
[0071] 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.
[0072] Unless otherwise indicated, all amounts are in % by volume
based on the total volume of the motor fuel composition.
[0073] 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.
[0074] In general, the total volume of ethanol (b) and
oxygen-containing additive (c) employed is from 0.15 to 25% by
volume, normally from about 0.5 to 25% by volume, preferably from
about 1 to 20% by volume, more preferably from 3 to 15% by volume,
and most preferably from 5 to 15% by volume.
[0075] The ratio of ethanol (b) to oxygen-containing additive (c)
in the motor fuel composition is thus generally from 1:150 to
400:1, and is more preferably from 1:10 to 10:1.
[0076] 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. %.
[0077] According to a preferred embodiment of the invention, to
obtain a motor fuel suitable for the operation of a standard spark
ignition internal combustion engine the aforesaid hydrocarbon
component, ethanol, and additional oxygen-containing component are
admixed to obtain the following properties of the resulting motor
fuel composition:
[0078] density at 15.degree. C. and at normal atmospheric pressure
of not less than 690 kg/m.sup.3;
[0079] oxygen content, based on the amount of oxygen-containing
components, of not more than 7% w/w of the motor fuel
composition;
[0080] 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;
[0081] dry vapor pressure equivalent (DVPE) essentially the same as
the DVPE of the source hydrocarbon component and preferably from 20
kPa to 120 kPa;
[0082] acid content of not more than 0.1% by weight HAc;
[0083] pH from 5 to 9;
[0084] aromatic hydrocarbons content of not more than 40% by
volume, including benzene, and for benzene alone, not more than 1%
by volume;
[0085] limits of evaporation of the liquid at normal atmospheric
pressure in percent of source volume of the motor fuel
composition:
1 initial boiling point, min 20.degree. C.; volume (at 70.degree.
C., min) of the liquid 25% by evaporated volume; volume (at
100.degree. C., min) of the liquid 50% by evaporated volume; volume
(at 150.degree. C., min) of the liquid 75% by evaporated volume;
volume (at 190.degree. C., min) of the liquid 95% by evaporated
volume; residue of distillation, max. 2% by volume; final boiling
point, max. 205.degree. C.; sulfur content of not more than 50
mg/kg; resins content of not more than 2 mg/100 ml.
[0086] According to a preferred embodiment of the method of the
invention, the ethanol component (b) is first added to the
hydrocarbon component (a) and then the oxygen-containing additive
(c) is added to a mixture of (b) and (a). Afterwards, the resulting
motor fuel composition should preferably be maintained at a
temperature not lower than -35.degree. C., for at least about one
hour. It is a feature of this invention that the components of the
motor fuel composition can be merely added to each other to form
the desired composition. It is generally not required to agitate or
otherwise provide any significant mixing to form the
composition.
[0087] According to a preferred embodiment of the invention to
obtain a motor fuel composition suitable for operating a standard
spark ignition internal combustion engine and with a minimal
harmful impact on environment, it is preferable to use
oxygen-containing component(s) originating from renewable raw
material(s).
[0088] Optionally, a component (d) can be used for further lowering
the vapor pressure of the fuel mixture of components (a), (b) and
(c). An individual hydrocarbon selected from a C.sub.6-C.sub.12
fraction of aliphatic or alicyclic saturated and unsaturated
hydrocarbons can be used as component (d). Preferably hydrocarbon
component (d) is selected from a C.sub.8-C.sub.11 fraction.
Suitable examples of (d) are benzene, toluene, xylene,
ethylbenzene, isopropylbenzene, isopropyltoluene, diethylbenzene,
isopropylxylene, tertbutylbenzene, tertbutyltoluene,
tertbutylxylene, cyclooctadiene, cyclooctatetraene, limonene,
isooctane, isononane, isodecane, isooctene, myrcene, allocymene,
tertbutylcyclohexane or similar hydrocarbons and mixtures
thereof.
[0089] Hydrocarbon component (d) can also be a fraction boiling at
100-200.degree. C., obtained in the distillation of oil, bituminous
coal resin, or synthesis-gas processing products.
[0090] 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) to be used as a fuel for a modified
spark ignition combustion engine.
[0091] The additive mixture of components (b) and (c) and,
optionally also component (d), can be used as a fuel for a modified
spark ignition combustion engine without the addition of the
hydrocarbon component (a) or conventional gasoline fuel.
[0092] However, to prepare a fuel for use in a conventional
gasoline engine, the additive mixture of components (b) and (c)
and, optionally also component (d), should be combined with a
conventional gasoline fuel. Sufficient amounts of the additive
mixture and the conventional gasoline fuel necessary to provide a
vapor pressure of the combination that is no greater than the vapor
pressure of the conventional gasoline fuel will be readily apparent
to a person skilled in the art.
[0093] 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 volume, and component (d) comprising at least one
C.sub.6-C.sub.12 hydrocarbon, more preferably C.sub.8-C.sub.11
hydrocarbon, in an amount up to 99% by volume, preferably from up
to 90%, more preferably up to 79.5%, and most preferably from 5 up
to 77% of the additive mixture. The additive mixture preferably has
a ratio of ethanol (b) to the sum of the other additive components
(c)+(d) from 1:200 to 200:1 by 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.
[0094] 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 admixing a corresponding
portion of the mixture of (b), (c) and (d) to component (a).
[0095] 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.
[0096] 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), and then this additive mixture can be
added to the hydrocarbon component (a), or vice versa. In this case
a certain amount of mixing may be required.
EXAMPLES
[0097] To prepare the blended motor fuel the following was used as
the components (b), (c), and (d):
[0098] (i) fuel grade ethanol purchased in Sweden at SEKAB and in
the USA from ADM Corp. and Williams;
[0099] (ii) oxygen-containing compounds, individual unsubstituted
hydrocarbons and mixtures thereof purchased in Germany from Merck
and in Russia from LUKOIL.
[0100] (iii) Naphtha, which is an oil straight run gasoline
containing aliphatic and alicyclic saturated and unsaturated
hydrocarbons. Alkylate, which is a hydrocarbon fraction consisting
almost completely of isoparaffine hydrocarbons obtained in
alkylation of isobutene by butanol. Alkylbenzene, which is a
mixture of aromatic hydrocarbons obtained in benzene alkylation.
Mostly, technical grade alkylbenzene comprises ethylbenzene,
propylbenzene, isopropylbenzene, butylbenzene and others.
[0101] 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.
[0102] The drivability testing was performed on a 1987 VOLVO 240 DL
according to the standard test method EU2000 NEDC EC 98/69.
[0103] 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 standardized EU tests include city
driving cycles and suburban driving cycles and require that
specific emission regulations be met. Exhaust emission analysis is
conducted with a constant volume sampling procedure and utilizes a
flame ionization detector for hydrocarbon determination. Exhaust
Emission Directive 91/441 EEC (Phase I) provides specific CO,
(HC+NO) and (PM) standards, while EU Fuel Consumption Directive
93/116 EEC (1996) implements consumption standards.
[0104] The testing was performed on a 1987 VOLVO 240 DL with a
B230F, 4-cylinder, 2.32 liter engine (No. LG4F20-87) developing 83
kW at 90 revolutions/second and a torque of 185 Nm at 46
revolutions/second.
EXAMPLE 1
[0105] Example 1 demonstrates the possibility of reducing the dry
vapor pressure equivalent of the ethanol-containing motor fuel for
the cases when gasolines with dry vapor pressure equivalent
according to ASTM D-5191 on a level of 90 kPa (about 13 psi) are
used as a hydrocarbon base.
[0106] 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.
[0107] FIG. 1 demonstrates the behavior of the DVPE of the
ethanol-containing motor fuel based on winter A95 gasoline. The
ethanol-containing motor fuel based on winter A92 and A98 used in
this example also demonstrate a similar behavior.
[0108] The source gasoline comprised aliphatic and alicyclic
C.sub.4-C.sub.12 hydrocarbons, which are both saturated and
unsaturated.
[0109] The winter A92 gasoline used had the following
specification:
[0110] DVPE=89.0 kPa
[0111] Anti-knock index 0.5(RON+MON)=87.7
[0112] The fuel 1-1 (not according to the invention) contained A92
winter gasoline and ethanol and had the following properties for
different ethanol contents:
[0113] A92:Ethanol=95:5% by volume
[0114] DVPE=94.4 kPa
[0115] 0.5(RON+MON)=89.1
[0116] A92:Ethanol=90:10% by volume
[0117] DVPE=94.0 kPa
[0118] 0.5(RON+MON)=90.2
[0119] The following different embodiments of the fuels 1-2 and 1-3
demonstrate the possibility of adjustment of the dry vapor pressure
equivalent (DVPE) of the ethanol-containing motor fuel based on
winter A92 gasoline.
[0120] The inventive fuel 1-2 contained A92 winter gasoline (a),
ethanol (b) and oxygen-containing additives (c) and had the
following properties for the different compositions:
[0121] A92:Ethanol:Isobutyl acetate=88.5:4.5:7% by volume
[0122] DVPE=89.0 kPa
[0123] 0.5(RON+MON)=89.9
[0124] A92:Ethanol:Isoamyl acetate=88:5:7% by volume
[0125] DVPE=88.6 kPa
[0126] 0.5(RON+MON)=89.0
[0127] A92:Ethanol:Diacetone alcohol=88.5:4.5:7% by volume
[0128] DVPE=89.0 kPa
[0129] 0.5(RON+MON)=89.65
[0130] AA92:Ethanol:Ethylacetoacetate=90.5:2.5:7% by volume
[0131] DVPE=89.0 kPa
[0132] 0.5(RON+MON)=87.8
[0133] A92:Ethanol:Isoamylpropionate=87.5:5.5:7% by volume
[0134] DVPE=88.7 kPa
[0135] 0.5(RON+MON)=90.4
[0136] The motor fuel compositions below demonstrate that it is not
always necessary to reduce the excess DVPE of the motor fuel
induced by presence of ethanol to the level of the DVPE of the
source gasoline. In some cases it is sufficient just to get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the winter
gasoline is 90 kPa.
[0137] A92:Ethanol:3-Heptanone=85:7.5:7.5% by volume
[0138] DVPE=90.0 kPa
[0139] 0.5(RON+MON)=89.9
[0140] A92:Ethanol:2,6-dimethyl-4-heptanol=85:8.5:6.5% by
volume
[0141] DVPE=90.0 kPa
[0142] 0.5(RON+MON)=90.3
[0143] A92:Ethanol:Diisobutyl ketone=85:7.5:7.5% by volume
[0144] DVPE=90.0 kPa
[0145] 0.5(RON+MON)=90.25
[0146] The inventive fuel 1-3 contained A92 winter gasoline (a),
ethanol (b), oxygen-containing additives (c) and hydrocarbons
C.sub.6-C.sub.12 (d), and had the following properties for the
different compositions:
[0147] A92:Ethanol:Isoamyl alcohol:Alkylate=79:9:2:10% by
volume
[0148] The boiling temperature of the alkylate is 100-130.degree.
C.
[0149] DVPE=88.5 kPa
[0150] 0.5(RON+MON)=90.25
[0151] A92:Ethanol:Isobutyl acetate:Naphtha=80:5:5:10% by
volume
[0152] The boiling temperature for the naphtha is 100-200.degree.
C.
[0153] DVPE=88.7 kPa
[0154] 0.5(RON+MON)=88.6
[0155] A92:Ethanol Tert-butanol:Naphtha=81:5:5:9% by volume
[0156] The boiling temperature for the naphtha is 100-200.degree.
C.
[0157] DVPE=87.5 kPa
[0158] 0.5(RON+MON)=89.6
[0159] The motor fuel compositions below demonstrate that it is not
always necessary to reduce the excess DVPE of the motor fuel
induced by presence of ethanol to the level of DVPE of the source
gasoline. In some cases it is sufficient just to get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the winter
gasoline is 90 kPa.
[0160] A92:Ethanol:Isoamyl
alcohol:Benzene:Ethylbenzene:Diethylbenzene=82.- 5:9.5:0.5:0.5:3:4%
by volume
[0161] DVPE=90 kPa
[0162] 0.5(RON+MON)=91.0
[0163] A92:Ethanol:Isobutyl acetate:Toluene=82.5:9.5:0.5:7.5% by
volume
[0164] DVPE=90 kPa
[0165] 0.5(RON+MON)=90.8
[0166] A92:Ethanol:Isobutanol:Isoamyl
alcohol:m-Xylene=82.5:9.2:0.2:0.6:7.- 5% by volume
[0167] DVPE=90 kPa
[0168] 0.5(RON+MON)=90.9
[0169] The following compositions 1-5 to 1-6 demonstrate the
possibility of adjustment of the dry vapor pressure equivalent
(DVPE) of the ethanol-containing motor fuel based on winter A98
gasoline.
[0170] The winter A98 gasoline had the following specification:
[0171] DVPE=89.5 kPa
[0172] Anti-knock index 0.5(RON+MON)=92.35
[0173] The comparative fuel 1-4 contained A98 winter gasoline and
ethanol and had the following properties for the different
compositions:
[0174] A98:Ethanol=95:5% by volume
[0175] DVPE=95.0 kPa
[0176] 0.5(RON+MON)=92.85
[0177] A98:Ethanol=90:10% by volume
[0178] DVPE=94.5 kPa
[0179] 0.5(RON+MON)=93.1
[0180] The fuel 1-5 contained A98 winter gasoline (a), ethanol (b),
and oxygen-containing additives (c) and had the following
properties for the different compositions:
[0181] A98:Ethanol:Isobutanol=84:9:7% by volume
[0182] DVPE=88.5 kPa
[0183] 0.5(RON+MON)=93.0
[0184] A98:Ethanol:Tert-butylacetate=84 :9:7% by volume
[0185] DVPE=89.5 kPa
[0186] 0.5(RON+MON)=93.3
[0187] A98:Ethanol:Benzyl alcohol=85:7.5:7.5% by volume
[0188] DVPE=89.5 kPa
[0189] 0.5(RON+MON)=93.05
[0190] A98:Ethanol:Cyclohexanone=85:7.5:7.5% by volume
[0191] DVPE=88.0 kPa
[0192] 0.5(RON+MON)=92.9
[0193] A98:Ethanol:dimethyl ketone=85:7.5:7.5% by volume
[0194] DVPE=89.0 kPa
[0195] 0.5(RON+MON)=92.85
[0196] A98:Ethanol:Methylpropyl ketone=85:7.5:7.5% by volume
[0197] DVPE=89.5 kPa
[0198] 0.5(RON+MON)=93.0
[0199] A98:Ethanol:Methylisobutyl ketone=85:7.5:7.5% by volume
[0200] DVPE=89.0 kPa
[0201] 0.5(RON+MON)=92.65
[0202] A98:Ethanol:3-heptanone=85:7.5 7.5% by volume
[0203] DVPE=89.5 kPa
[0204] 0.5(RON+MON)=92.0
[0205] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the winter gasoline is 90 kPa.
[0206] A98:Ethanol:Methylisobutyl ketone=85:8:7% by volume
[0207] DVPE=90.0 kPa
[0208] 0.5(RON+MON)=92.7
[0209] A98:Ethanol:Cyclohexanone=85:8.5:6.5% by volume
[0210] DVPE=90.0 kPa
[0211] 0.5(RON+MON)=93.0
[0212] A98:Ethanol:Methylphenol=85:8:7% by volume
[0213] DVPE=90.0 kPa
[0214] 0.5(RON+MON)=93.05
[0215] The fuel 1-6 contained A98 winter gasoline (a), ethanol (b),
oxygen-containing additives (c), and C.sub.6-C.sub.12 hydrocarbons
(d) and had the following properties for the different
compositions:
[0216] A98:Ethanol:Isoamyl alcohol:Isooctane=80:5:5:10% by
volume
[0217] DVPE=82.0 kPa
[0218] 0.5(RON+MON)=93.2
[0219] A98:Ethanol:Isoamyl alcohol:m-Isopropyl
toluene=78.2:6.1:6.1:9.6% by volume
[0220] DVPE=81.0 kPa
[0221] 0.5(RON+MON)=93.8
[0222] A98:Ethanol:Isobutanol:Naphtha=80:5:5:10% by volume
[0223] The boiling point of the naphtha is 100-200.degree. C.
[0224] DVPE=82.5 kPa
[0225] 0.5(RON+MON)=92.35
[0226] A98:Ethanol:Isobutanol:Naphtha:m-Isopropyl
toluene=80:5:5:5:5% by volume
[0227] The boiling point of the naphtha is 100-200.degree. C.
[0228] DVPE=82.0 kPa
[0229] 0.5(RON+MON)=93.25
[0230] A98:Ethanol:Tert-butyl acetate:Naphtha=83:5:5:7% by
volume
[0231] The boiling temperature of the naphtha is 100-200.degree.
C.
[0232] DVPE=82.1 kPa
[0233] 0.5(RON+MON)=92.5
[0234] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the winter gasoline is 90 kPa.
[0235] A98:Ethanol:Isoamyl alcohol:Isooctane=85:5:5:5% by
volume
[0236] DVPE=90.0 kPa
[0237] 0.5(RON+MON)=93.3
[0238] A98:Ethanol:Isobutanol:Naphtha=85:5:5:5% by volume
[0239] The boiling temperature of the naphtha is 100-200.degree.
C.
[0240] DVPE=90.0 kPa
[0241] 0.5(RON+MON)=93.0
[0242] A98:Ethanol:Isobutanol:Isopropyl xylene=85:9.5:0.5:5% by
volume
[0243] DVPE=90 kPa
[0244] 0.5(RON+MON)=93.1
[0245] The motor fuel compositions below demonstrate that it might
be necessary to reduce the excess DVPE of the motor fuel caused by
presence of ethanol below the level of DVPE of the source gasoline.
Normally, this is required when DVPE of the source gasoline is
higher than the limits of the regulations in force towards
corresponding gasoline. In this way, for example, it is possible to
transform the winter grade gasoline into the summer grade gasoline.
The DVPE level for the summer gasoline is 70 kPa.
[0246] A98:Ethanol:Isobutanol:Isooctane:Naphtha=60:9.5:0.5:15:15%
by volume
[0247] The boiling point of the naphtha is 100-200.degree. C.
[0248] DVPE=70 kPa
[0249] 0.5(RON+MON)=92.85
[0250] A98:Ethanol:Isobutanol:Alkylate:Naphtha=60:9.5:0.5:15:15% by
volume
[0251] The boiling point of the naphtha is 100-200.degree. C.
[0252] The boiling point of the alkylate is 100-130.degree. C.
[0253] DVPE=70 kPa
[0254] 0.5(RON+MON)=92.6
[0255] A98:Ethanol:Tert-butyl acetate:Naphtha=60:9:3:28% by
volume
[0256] The boiling point of the naphtha is 100-200.degree. C.
[0257] DVPE=70 kPa
[0258] 0.5(RON+MON)=91.4
[0259] 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.
[0260] The winter A95 gasoline had the following specification:
[0261] DVPE=89.5 kPa
[0262] Anti-knock index 0.5(RON+MON)=90.1
[0263] The testing in accordance with the standard test method EU
2000 NEDC EC 98/69 as described above demonstrated the following
results:
2 CO (carbon monoxide) 2.13 g/km; HC (hydrocarbons) 0.280 g/km;
NO.sub.x (nitrogen oxides) 0.265 g/km; CO.sub.2 (carbon dioxide)
227.0 g/km; NMHC* 0.276 g/km; Fuel consumption, F.sub.c (1/100 km)
9.84 *Non-methane hydrocarbons.
[0264] The comparative fuel 1-7 contained A95 winter gasoline and
ethanol, and had the following properties for the different
compositions:
[0265] A95:Ethanol=95%:5% by volume
[0266] DVPE=94.9 kPa
[0267] 0.5(RON+MON)=91.6
[0268] A95:Ethanol=90%:10% by volume (referred to as RFM1
below)
[0269] DVPE=94.5 kPa
[0270] 0.5(RON+MON)=92.4
[0271] The testing of the reference fuel mixture (RFM1)
demonstrated the following results, as compared to the winter A95
gasoline:
3 CO -15.0%; HC -7.3%; NO.sub.x +15.5%; CO.sub.2 +2.4%; NMHC*
-0.5%; Fuel consumption, F.sub.c (1/100 km) 0.047 *Non-methane
hydrocarbons. "-" represents a reduction in emission, while "+"
represents an increase in emission.
[0272] 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 different compositions:
[0273] A95:Ethanol:Diisoamyl ether=86:8:6% by volume
[0274] DVPE=87.5 kPa
[0275] 0.5(RON+MON)=90.6
[0276] A95:Ethanol:Isobutyl acetate=88:5:7% by volume
[0277] DVPE=87.5 kPa
[0278] 0.5(RON+MON)=91.85
[0279] A95 Ethanol:Isoamylpropionate=88:5:7% by volume
[0280] DVPE=87.0 kPa
[0281] 0.5(RON+MON)=91.35
[0282] A95:Ethanol:Isoamylacetate=88:5:7% by volume
[0283] DVPE=87.5 kPa
[0284] 0.5(RON+MON)=91.25
[0285] A95:Ethanol:2-octanone=88:5:7% by volume
[0286] DVPE=87.0 kPa
[0287] 0.5(RON+MON)=90.5
[0288] A95:Ethanol:Tetrahydrofurfuryl alcohol=88:5:7% by volume
[0289] DVPE=87.5 kPa
[0290] 0.5(RON+MON)=90.6
[0291] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the winter gasoline is 90 kPa.
[0292] A95:Ethanol:Diisoamyl ether=87:9:4% by volume
[0293] DVPE=90.0 kPa
[0294] 0.5(RON+MON)=91.0
[0295] A95:Ethanol:Isoamyl acetate=88:7:5% by volume
[0296] DVPE=90.0 kPa
[0297] 0.5(RON+MON)=91.3
[0298] A95:Ethanol:Tetrahydrofurfuryl alcohol=88:7:5% by volume
[0299] DVPE=90.0 kPa
[0300] 0.5(RON+MON)=90.8
[0301] The fuel 1-9 contained A95 winter gasoline (a), ethanol (b),
the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0302] A95:Ethanol:Isoamyl alcohol:Alkylate=83.7:5:2:9.3% by
volume
[0303] The boiling temperature of the alkylate is 100-130.degree.
C.
[0304] DVPE=88.0 kPa
[0305] 0.5(RON+MON)=91.65
[0306] A95:Ethanol:Isoamyl alcohol:Naphtha=83.7:5:2:9.3% by
volume
[0307] The boiling temperature of the naphtha is 100-200.degree.
C.
[0308] DVPE=88.5 kPa
[0309] 0.5(RON+MON)=90.8
[0310] A95:Ethanol:Isobutyl acetate:Alkylate=81:5:5:9% by
volume
[0311] The boiling temperature of the alkylate is 100-130.degree.
C.
[0312] DVPE=87.0 kPa
[0313] 0.5(RON+MON)=92.0
[0314] A95:Ethanol:Isobutyl acetate:Naphtha=81:5:5:9% by volume
[0315] The boiling temperature of the naphtha is 100-200.degree.
C.
[0316] DVPE=87.5 kPa
[0317] 0.5(RON+MON)=91.1
[0318] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the winter gasoline is 90 kPa.
[0319] A95:Ethanol:Isoamyl alcohol:Xylene=80:9.5:0.5:10% by
volume
[0320] DVPE=90.0 kPa
[0321] 0.5(RON+MON)=92.1
[0322] A95:Ethanol:Isobutanol:Isoamyl
alcohol:Naphtha=80:9.2:0.2:0.6:10% by volume
[0323] The boiling temperature of the naphtha is 100-200.degree.
C.
[0324] DVPE=90.0 kPa
[0325] 0.5(RON+MON)=91.0
[0326] A95:Ethanol:Isobutanol:Isoamyl
alcohol:Naphtha:Alkylate=80:9.2:0.2:- 0.6:5:5% by volume
[0327] The boiling temperature of the naphtha is 100-200.degree.
C.
[0328] The boiling point of the alkylate is 100-130.degree. C.
[0329] DVPE=90.0 kPa
[0330] 0.5(RON+MON)=91.6
[0331] The motor fuel compositions below demonstrate that it might
be necessary to reduce the excess DVPE of the motor fuel caused by
presence of ethanol below the level of DVPE of the source gasoline.
Normally, this is required when DVPE of the source gasoline is
higher than the limits of the regulations in force towards
corresponding gasoline. In this way, for example, it is possible to
transform the winter grade gasoline into the summer grade gasoline.
The DVPE level for the summer gasoline is 70 kPa.
[0332] A95:Ethanol:Isobutanol:Isoamyl
alcohol:Naphtha:Isooctane=60:9.2:0.2- :0.6:15:15% by volume
[0333] The boiling temperature of the naphtha is 100-200.degree.
C.
[0334] DVPE=70.0 kPa
[0335] 0.5(RON+MON)=91.8
[0336] A95:Ethanol:Tert-butyl acetate:Naphtha=60:9:1:30% by
volume
[0337] The boiling temperature of the naphtha is 100-200.degree.
C.
[0338] DVPE=70.0 kPa
[0339] 0.5(RON+MON)=90.4
[0340] The fuel 1-10 contains 75% by volume A95 winter gasoline,
9.6% by volume ethanol, 0.4% by volume isobutyl alcohol, 4.5% by
volume m-isopropyl toluene and 10.5% by volume naphtha with boiling
temperature of 100-200.degree. C. This fuel formulation
demonstrates the possibility of decreasing the DVPE, increasing the
octane number, decreasing the level of toxic emissions in the
exhaust and decreasing the fuel consumption in comparison with the
reference mixture of gasoline and ethanol (RFM 1). The motor fuel
composition has the following properties:
4 density at 15.degree. C., according to ASTM D 749.2 kg/m.sup.3;
4052 initial boiling point, according to 29.degree. C.; ASTM D-86
vaporizable portion - 70.degree. C. 47.6% by volume; vaporizable
portion - 100.degree. C. 55.6% by volume; vaporizable portion -
150.degree. C. 84.2% by volume; vaporizable portion - 180.degree.
C. 97.5% by volume; final boiling point 194.9.degree. C.;
evaporation residue 1.3% by volume; loss by evaporation 1.6% by
volume; oxygen content, according to ASTM D- 3.7% w/w; 4815
acidity, according to ASTM D-1613 0.004; weight % HAc pH, according
to ASTM D-1287 6.6; sulfur content, according to ASTM D- 18 mg/kg;
5453 gum content, according to ASTM D-381 1 mg/100 ml; water
content, according to ASTM D- 0.03% w/w; 6304 aromatics, according
to SS 155120, 30.2% by including benzene volume; benzene alone,
according to EN 238 0.7% by volume; DVPE, according to ASTM D 5191
89.0 kPa; anti-knock index 0.5 (RON + MON), 92.6 according to ASTM
D 2699-86 and ASTM D-2700-86
[0341] The motor fuel formulation 1-10 was tested in accordance
with the standard test method EU 2000 NEDC EC 98/69 and the
following results, as compared to winter A95 gasoline, were
obtained:
5 CO -21%; HC -9%; NO.sub.x +12.8%; CO.sub.2 +2.38%; NMHC -6.4%;
Fuel consumption, F.sub.c (1/100 km) +3.2%
[0342] 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 obtained when other oxygen-containing
compounds of this invention are substituted for the additives of
the examples 1-1 to 1-10.
[0343] 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.degree. C. All the above formulations were prepared
without the use of any mixing devices.
[0344] It was established that is was possible to employ an
additive mixture of the oxygen-containing additive other than
ethanol (c) and ethanol (b) for formulating the ethanol-containing
motor fuels for standard internal combustion spark ignition engines
meeting standard requirements for gasolines, regarding their vapor
pressure and anti-knock stability.
[0345] The following fuel compositions demonstrate such a
possibility.
[0346] A mixture comprising 50% of ethanol and 50% of isoamyl
alcohol was mixed in different proportions with winter grade
gasolines, the dry vapor 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.
[0347] A92:Ethanol:Isoamyl alcohol=87:6.5:6.5% by volume
[0348] DVPE=89.0 kPa
[0349] 0.5(RON+MON)=90.15
[0350] A95:Ethanol:Isoamyl alcohol=86:7.0:7.0% by volume
[0351] DVPE=89.3 kPa
[0352] 0.5(RON+MON)=92.5
[0353] A98:Ethanol:Isoamyl alcohol=85:7.5:7.5% by volume
[0354] DVPE=86.5 kPa
[0355] 0.5(RON+MON)=92.9
[0356] FIG. 2 shows the behavior of the dry vapor pressure
equivalent (DVPE) as a function of the ethanol content when
admixing the additive mixture comprising 33.3% of ethanol and 66.7%
of tert-pentanol with A95 winter gasoline. FIG. 2 demonstrates that
varying of the ethanol content in gasoline within the range from 0
to 11% does not induce an increase of the vapor pressure for these
compositions higher than the requirement of the standard for DVPE
of the winter grade gasolines, which is 90 kPa.
[0357] Similar DVPE behavior 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.
[0358] The effect of the reduction of the vapor pressure of the
ethanol-containing gasolines while increasing the ethanol content
in the resulting composition from 0 to 11% by volume was also
observed when part of the oxygen-containing additive was replaced
by C.sub.6-C.sub.12 hydrocarbons (component (d)). The compositions
below demonstrate the effect achieved by means of the
invention.
[0359] An additive mixture comprising 40% by volume of ethanol, 10%
by volume of isobutanol and 50% by volume of isopropyltoluene was
mixed with winter gasoline with DVPE not higher than 90 kPa. The
different obtained compositions had the following properties:
[0360] A92:Ethanol:Isobutanol:Isopropyltoluene=85:6:1.5:7.5% by
volume
[0361] DVPE=84.9 kPa
[0362] 0.5(RON+MON)=93.9
[0363] A95:Ethanol:Isobutanol:Isopropyltoluene=80:8:2:10% by
volume
[0364] DVPE=84.0 kPa
[0365] 0.5(RON+MON)=94.1
[0366] A98:Ethanol:Isobutanol:Isopropyltoluene=86:5.6:1.4:7% by
volume
[0367] DVPE=85.5 kPa
[0368] 0.5(RON+MON)=93.8
[0369] Similar results were obtained when other oxygen-containing
compounds and also C.sub.6-C.sub.12 hydrocarbons of the present
invention were used in the ratio of the invention to prepare the
additive mixture, which was then used for preparation of the
ethanol-containing gasolines. These gasolines entirely meet the
requirements towards the motor fuels used in the standard spark
ignition engines.
EXAMPLE 2
[0370] Example 2 demonstrates the possibility to reduce the dry
vapor pressure equivalent of the ethanol-containing motor fuel for
the cases when gasolines with a dry vapor pressure equivalent
according to ASTM D-5191 on a level of 70 kPa (about 10 psi) are
used as a hydrocarbon base.
[0371] 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.
[0372] The source gasoline comprised aliphatic and alicyclic
C.sub.4-C.sub.12 hydrocarbons, including saturated and unsaturated
ones.
[0373] FIG. 1 shows the behavior of the DVPE of the
ethanol-containing motor fuel based on summer A95 gasoline. The
ethanol-containing motor fuels based on winter A92 and A98
gasolines, respectively, demonstrated similar behavior.
[0374] The following fuels 2-2 and 2-3 demonstrate the possibility
of adjusting the dry vapor pressure equivalent (DVPE) of the
ethanol-containing motor fuel based on summer A92 gasoline.
[0375] The summer A92 gasoline had the following properties:
[0376] DVPE=70.0 kPa
[0377] Anti-knock index 0.5(RON+MON)=87.5
[0378] The comparative fuel 2-1 contained A92 summer gasoline and
ethanol, and had the following properties for the different
compositions:
[0379] A92:Ethanol=95:5% by volume
[0380] DVPE=77.0 kPa
[0381] 0.5(RON+MON)=89.3
[0382] A92:Ethanol=90:10% by volume
[0383] DVPE=76.5 kPa
[0384] 0.5(RON+MON)=90.5
[0385] The fuel 2-2 contained A92 summer gasoline (a), ethanol (b),
and the oxygen-containing additives (c) and had the following
properties for the different compositions:
[0386] A92:Ethanol:Isoamyl alcohol=85:6.5:6.5% by volume
[0387] DVPE=69.8 kPa
[0388] 0.5(RON+MON)=90.3
[0389] A92:Ethanol:Isobutanol=80:10:10% by volume
[0390] DVPE=67.5 kPa
[0391] 0.5(RON+MON)=90.8
[0392] A92:Ethanol:Diethylcarbinol=85:6.5:6.5% by volume
[0393] DVPE=69.6 kPa
[0394] 0.5(RON+MON)=90.5
[0395] A92:Ethanol:Diisobutyl ketone=85.5:7.5:7% by volume
[0396] DVPE=69.0 kPa
[0397] 0.5(RON+MON)=90.0
[0398] A92:Ethanol:Diisobutyl ether=85 8:7% by volume
[0399] DVPE=68.9 kPa
[0400] 0.5(RON+MON)=90.1
[0401] A92:Ethanol:Di-n-butyl ester=85:8:7% by volume
[0402] DVPE=68.5 kPa
[0403] 0.5(RON+MON)=88.5
[0404] A92:Ethanol:Isobutylacetate=88:5:7% by volume
[0405] DVPE=69.5 kPa
[0406] 0.5(RON+MON)=89.5
[0407] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the summer gasoline is 70 kPa.
[0408] A92:Ethanol:Isobutanol=87.5:10:7.5% by volume
[0409] DVPE=70.0 kPa
[0410] 0.5(RON+MON)=90.6
[0411] A92:Ethanol:Di-n-butyl ether=85:9:6% by volume
[0412] DVPE=70.0 kPa
[0413] 0.5(RON+MON)=89.2
[0414] A92:Ethanol:Diisobutyl ketone=85:8:7% by volume
[0415] DVPE=70.0 kPa
[0416] 0.5(RON+MON)=90.4
[0417] The fuel 2-3 contained A92 summer gasoline (a), ethanol (b),
the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0418] A92:Ethanol:Methylethyl ketone:Isooctane=80:9.5:0.5:10% by
volume
[0419] DVPE=69.0 kPa
[0420] 0.5(RON+MON)=91.0
[0421] A92:Ethanol:Isobutanol:Isooctane=80:9.5:0.5:10% by
volume
[0422] DVPE=69.0 kPa
[0423] 0.5(RON+MON)=91.1
[0424] A92:Ethanol:Isobutanol:Isononane=80:9.5:0.5:10% by
volume
[0425] DVPE=68.8 kPa
[0426] 0.5(RON+MON)=91.0
[0427] A92:Ethanol:Isobutanol:Isodecane=80:9.5:0.5:10% by
volume
[0428] DVPE=68.5 kPa
[0429] 0.5(RON+MON)=90.8
[0430] A92:Ethanol:Isobutanol:Isooctene=80:9.5:0.5:10% by
volume
[0431] DVPE=68.9 kPa
[0432] 0.5(RON+MON)=91.2
[0433] A92:Ethanol:Isobutanol:Toluene=80:9.5:0.5:10% by volume
[0434] DVPE=68.5 kPa
[0435] 0.5(RON+MON)=91.4
[0436] A92:Ethanol:Isobutanol:Naphtha=80:9.5:0.5:10% by volume
[0437] The boiling temperature for the naphtha is 100-200.degree.
C.
[0438] DVPE=67.5 kPa
[0439] 0.5(RON+MON)=90.4
[0440] A92:Ethanol:Isobutanol:Naphtha:Toluene=80:9.5:0.5:5:5% by
volume
[0441] The boiling temperature for the naphtha is 100-200.degree.
C.
[0442] DVPE=67.5 kPa
[0443] 0.5(RON+MON)=90.9
[0444]
A92:Ethanol:Isobutanol:Naphtha:Isopropyltoluene=80:9.5:0.5:5:5% by
volume
[0445] The boiling temperature for the naphtha is 100-200.degree.
C.
[0446] DVPE=67.5 kPa
[0447] 0.5(RON+MON)=91.2
[0448] 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 get it in compliance with
the requirements of the regulations in force towards corresponding
gasoline. The DVPE level for the summer gasoline is 70 kPa.
[0449] A92:Ethanol:Isobutanol:Isodecane=82.5:9.5:0.5:7.5% by
volume
[0450] DVPE=70.0 kPa
[0451] 0.5(RON+MON)=90.85
[0452] A92:Ethanol:Isobutanol:Tertbutylbenzene=82.5:9.5:0.5:7.5% by
volume
[0453] DVPE=70.0 kPa
[0454] 0.5(RON+MON)=91.5
[0455] A92:Ethanol:Isobutanol:Isoamyl
alcohol:Naphtha:Tertbutyltoluene=82.- 5:9.2:0.2:0.6:5:2.5% by
volume
[0456] DVPE=70.0 kPa
[0457] 0.5(RON+MON)=91.1
[0458] The following fuels 2-5 and 2-6 demonstrate the possibility
of adjusting the dry vapor pressure equivalent (DVPE) of the
ethanol-containing motor fuel based on summer A98 gasoline.
[0459] The summer A98 gasoline had the following specification:
[0460] DVPE=69.5 kPa
[0461] Anti-knock index 0.5(RON+MON)=92.5
[0462] The comparative fuel 2-4 contained A98 summer gasoline and
ethanol, and had the following properties for the different
compositions:
[0463] A98:Ethanol=95:5% by volume
[0464] DVPE=76.5 kPa
[0465] 0.5(RON+MON)=93.3
[0466] A98:Ethanol=90:10% by volume
[0467] DVPE=76.0 kPa
[0468] 0.5(RON+MON)=93.7
[0469] The fuel 2-5 contained A98 summer gasoline (a), ethanol (b)
and the oxygen-containing additives (c), and had the following
properties for the different compositions:
[0470] A98:Ethanol:Isobutanol=85:7.5:7.5% by volume
[0471] DVPE=69.5 kPa
[0472] 0.5(RON+MON)=93.5
[0473] A98:Ethanol:Diisobutyl ketone=83:9.5:7.5% by volume
[0474] DVPE=69.0 kPa
[0475] 0.5(RON+MON)=93.9
[0476] A98:Ethanol:Isobutyl acetate=88:5:7% by volume
[0477] DVPE=69.5 kPa
[0478] 0.5(RON+MON)=93.4
[0479] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the summer
gasoline is 70 kPa.
[0480] A98:Ethanol:Isobutanol=85:8:7% by volume
[0481] DVPE=70.0 kPa
[0482] 0.5(RON+MON)=93.7
[0483] A98:Ethanol:Tert-pentanol=90:5:5% by volume
[0484] DVPE=70.0 kPa
[0485] 0.5(RON+MON)=93.8
[0486] The fuel 2-6 contained A98 summer gasoline (a), ethanol (b),
the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0487] A98:Ethanol:Isobutanol:Isooctane=80:9.5:0.5:10% by
volume
[0488] DVPE=69.0 kPa
[0489] 0.5(RON+MON)=93.7
[0490] A98:Ethanol:Isopropanol:Alkylbenzene=80:5:5:10% by
volume
[0491] DVPE=68.5 kPa
[0492] 0.5(RON+MON)=94.0
[0493] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the summer
gasoline is 70 kPa.
[0494] A98:Ethanol:Isobutanol:Isooctane=81.5:9.5:0.5:8.5% by
volume
[0495] DVPE=70.0 kPa
[0496] 0.5(RON+MON)=93.5
[0497] A98:Ethanol:Tert-butanol:Limonene=86:7:4:4% by volume
[0498] DVPE=70.0 kPa
[0499] 0.5(RON+MON)=93.6
[0500] The following fuels 2-8 to 2-10 demonstrate the possibility
of adjusting the dry vapor pressure equivalent (DVPE) of the
ethanol-containing motor fuel based on summer A95 gasoline.
[0501] The summer A95 gasoline had the following specification:
[0502] DVPE=68.5 kPa
[0503] Anti-knock index 0.5(RON+MON)=89.8
[0504] The testing performed as above demonstrated for the summer
A95 gasoline the following results:
6 CO (carbon monoxide) 2.198 g/km; HC (hydrocarbons) 0.245 g/km;
NO.sub.x (nitrogen oxides) 0.252 g/km; CO.sub.2 (carbon dioxide)
230.0 g/km; NMHC* 0.238 g/km; Fuel consumption, F.sub.c (1/100 km)
9.95 *Non-methane hydrocarbons.
[0505] The comparative fuel 2-7 contained A95 summer gasoline and
ethanol, and had the following properties for the different
compositions:
[0506] A95:Ethanol=95%:5% by volume
[0507] DVPE=75.5 kPa
[0508] 0.5(RON+MON)=90.9
[0509] A95:Ethanol=90%:10% by volume (also referred to as RFM 2
below)
[0510] DVPE=75.0 kPa
[0511] 0.5(RON+MON)=92.25
[0512] The testing of the reference fuel mixture (RFM 2)
demonstrated the following results, as compared to summer A95
gasoline:
7 CO -9.1%; HC -4.5%; NO.sub.x +7.3%; CO.sub.2 +4.0%; NMHC* -4.4%;
Fuel consumption, F.sub.c (1/100 km) +3.6% "-" represents a
reduction in emission, while "+" represents an increase in
emission
[0513] The fuel 2-8 contained A95 summer gasoline and the
oxygen-containing additives and had the following properties for
the different compositions:
[0514] A95:Ethanol:Isoamyl alcohol=85:7.5:7.5% by volume
[0515] DVPE=68.5 kPa
[0516] 0.5(RON+MON)=92.2
[0517] A95:Ethanol:Diisoamyl ether=86:8 6% by volume
[0518] DVPE=66.5 kPa
[0519] 0.5(RON+MON)=90.2
[0520] A95:Ethanol:Isobutylacetate=88:5:7% by volume
[0521] DVPE=67.0 kPa
[0522] 0.5(RON+MON)=92.0
[0523] A95:Ethanol:Tert-butanol=88:5:7% by volume
[0524] DVPE=68.4 kPa
[0525] 0.5(RON+MON)=92.6
[0526] A95:Ethanol:Tert-pentanol=90:5:5% by volume
[0527] DVPE=68.5 kPa
[0528] 0.5(RON+MON)=92.2
[0529] A95:Ethanol:Isopropanol=80:10:10% by volume
[0530] DVPE=68.5 kPa
[0531] 0.5(RON+MON)=92.8
[0532] A95:Ethanol:4-methyl-2-pentanol=85:8:7% by volume
[0533] DVPE=66.0 kPa
[0534] 0.5(RON+MON)=91.0
[0535] A95:Ethanol:Dimethyl ketone=85:8:7% by volume
[0536] DVPE=68.0 kPa
[0537] 0.5(RON+MON)=92.2
[0538] A95:Ethanol:Trimethylcyclohexanone=85:8:7% by volume
[0539] DVPE=67.0 kPa
[0540] 0.5(RON+MON)=91.8
[0541] A95:Ethanol:Methyltertamyl ether=80:8:12% by volume
[0542] DVPE=68.0 kPa
[0543] 0.5(RON+MON)=93.8
[0544] A95:Ethanol:n-Butylacetate=87:6.5:6.5% by volume
[0545] DVPE=68.0 kPa
[0546] 0.5(RON+MON)=90.1
[0547] A95:Ethanol:Isobutylisobutyrate=90:5:5% by volume
[0548] DVPE=68.5 kPa
[0549] 0.5(RON+MON)=90.0
[0550] A95:Ethanol:Methylacetoacetate=85:7:8% by volume
[0551] DVPE=68.5 kPa
[0552] 0.5(RON+MON)=89.9
[0553] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the summer
gasoline is 70 kPa.
[0554] A95:Ethanol:4-methyl-2-pentanol=85:10:5% by volume
[0555] DVPE=70.0 kPa
[0556] 0.5(RON+MON)=91.6
[0557] A95:Ethanol:Isobutylisobutyrate=90:6:4% by volume
[0558] DVPE=70.0 kPa
[0559] 0.5(RON+MON)=90.5
[0560] The fuel 2-9 contained A95 summer gasoline (a), ethanol (b),
the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0561] A95:Ethanol:Tert-pentanol:Alkylbenzene=80:7:4:9% by
volume
[0562] DVPE=67.5 kPa
[0563] 0.5(RON+MON)=93.6
[0564] A95:Ethanol:Tert-butanol:Alkylbenzene=80:7:4:9% by
volume
[0565] DVPE=68.0 kPa
[0566] 0.5(RON+MON)=93.8
[0567] A95:Ethanol:Propanol:Xylene=80:9.5:0.5:10% by volume
[0568] DVPE=68.0 kPa
[0569] 0.5(RON+MON)=93.1
[0570] A95:Ethanol:Diethylketone:Xylene=80:9.5:0.5:10% by
volume
[0571] DVPE=68.0 kPa
[0572] 0.5(RON+MON)=93.2
[0573]
A95:Ethanol:Isobutanol:Naphtha:Isopropyltoluene=80:9.5:0.5:5:5% by
volume
[0574] The boiling temperature for the naphtha is 100-170.degree.
C.
[0575] DVPE=68.0 kPa
[0576] 0.5(RON+MON)=92.4
[0577] A95:Ethanol:Isobutanol:Naphtha:Alkylate=80:9.5:0.5:5:5% by
volume
[0578] The boiling temperature for the naphtha is 100-170.degree.
C.
[0579] The boiling temperature for the alkylate is 100-130.degree.
C.
[0580] DVPE=68.5 kPa
[0581] 0.5(RON+MON)=92.2
[0582] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the summer
gasoline is 70 kPa.
[0583] A95:Ethanol:Isobutanol:Isoamyl
alcohol:Xylene=82.5:9.2:0.2:0.6:7.5% by volume
[0584] DVPE=70.0 kPa
[0585] 0.5(RON+MON)=93.0
[0586] A95:Ethanol:Isobutanol:Isoamyl
alcohol:Cyclooctadiene=82.5:9.2:0.2:- 0.6:7.5% by volume
[0587] DVPE=70.0 kPa
[0588] 0.5(RON+MON)=92.1
[0589] The fuel formulation 2-10 contained 81.5% by volume of
[0590] 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 vapor 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:
8 density at 15.degree. C., according to ASTM 754.1 kg/m.sup.3;
D-4052 initial boiling point, according to ASTM 26.6.degree. C.;
D-86 vaporizable portion - 70.degree. C. 45.2% by volume;
vaporizable portion - 100.degree. C. 56.4% by volume; vaporizable
portion - 150.degree. C. 88.8% by volume; vaporizable portion -
180.degree. C. 97.6% by volume; final boiling point 186.3.degree.
C.; evaporation residue 1.6% by volume; loss by evaporation 0.1% by
volume; oxygen content, according to ASTM 3.56% w/w; D-4815
acidity, according to ASTM D-1613 0.007; weight % HAc pH, according
to ASTM D-1287 8.9; sulfur content, according to ASTM 16 mg/kg;
D-5453 gum content, according to ASTM D- <1 mg/100 ml; 381 water
content, according to ASTM 0.12% w/w; D-6304 aromatics, according
to SS 155120, 30.3% by including benzene volume; benzene alone,
according to EN 238 0.8% by volume; DVPE, according to ASTM D-5191
68.5 kPa; anti-knock index 0.5 (RON + MON), 92.7 according to ASTM
D-2699-86 and ASTM D-2700-86
[0591] 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:
9 CO -0.18% HC -8.5%; NO.sub.x +5.3%; CO.sub.2 +2.8%; NMHC -9%;
Fuel consumption, F.sub.c (1/100 km) +3.1%
[0592] 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 obtained when other oxygen-containing
additives of the invention are substituted for the additives of the
examples 2-1 to 2-10.
[0593] To prepare all the above fuel formulations 2-1 to 2-10 of
this motor fuel composition, initially gasoline was mixed with
ethanol, and then added the corresponding oxygen-containing
additive was added to the 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.degree. C. All the above
formulations were prepared without the use of any mixing
devices.
[0594] The use of an additive mixture comprising ethanol and
oxygen-containing compounds other than ethanol for preparation of
the ethanol-containing gasolines was accomplished with summer grade
gasolines. The fuel compositions below demonstrate the possibility
to obtain the ethanol-containing gasolines meeting standard
requirements towards summer grade gasolines, including vapor
pressure of not higher than 70 kPa.
[0595] FIG. 2 shows the behavior of the dry vapor pressure
equivalent (DVPE) as a function of the ethanol content while mixing
summer A95 gasoline with the additive mixture 3 comprising 35% by
volume of ethanol, 5% by volume of isoamyl alcohol, and 60% by
volume of naphtha boiling at temperatures between 100-170.degree.
C. FIG. 2 demonstrates that varying of the ethanol content in
gasoline within the range from 0 to 20% does not induce an increase
of the vapor pressure for these compositions higher than the
requirement of the standard for DVPE of the summer grade gasolines,
which is 70 kPa. Similar DVPE behavior 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.degree. C.
[0596] The ratio between ethanol and the oxygen-containing compound
other than ethanol in the additive mixture, which is used for
preparation of the ethanol-containing gasolines, is of substantial
importance. The ratio between the components of the additive
established by the present invention enables the adjusting of the
vapor pressure of the ethanol-containing gasolines over a wide
range.
[0597] The compositions below demonstrate the possibility to employ
the additive mixtures with both high and low ethanol content. An
additive mixture comprising 92% by volume of ethanol, 6% by volume
of isoamyl alcohol, and 2% by volume of isobutanol was mixed with
summer grade gasoline. The obtained compositions had the following
properties:
[0598] A92:Ethanol:Isoamyl alcohol:Isobutanol=80:18.4:1.2:0.4% by
volume
[0599] DVPE=70.0 kPa
[0600] 0.5(RON+MON)=90.3
[0601] A95:Ethanol:Isoamyl alcohol:Isobutanol=82:16.56:1.08:0.36%
by volume
[0602] DVPE=69.9 kPa
[0603] 0.5(RON+MON)=92.6
[0604] A98:Ethanol:Isoamyl alcohol:Isobutanol=78:20.24:1.32:0.44%
by volume
[0605] DVPE=70.0 kPa
[0606] 0.5(RON+MON)=94.5
[0607] An additive mixture comprising 25% by volume of ethanol, 60%
by volume of isoamyl alcohol, and 15% by volume of isobutanol was
mixed with summer grade gasoline. The obtained compositions had the
following properties:
[0608] A92:Ethanol:Isoamyl alcohol:Isobutanol=80:5:12:3% by
volume
[0609] DVPE=66.0 kPa
[0610] 0.5(RON+MON)=88.6
[0611] A95:Ethanol:Isoamyl alcohol:Isobutanol=84:4:9.6:2.4% by
volume
[0612] DVPE=65.5 kPa
[0613] 0.5(RON+MON)=91.3
[0614] A98:Ethanol:Isoamyl alcohol:Isobutanol=86:3.5:8.4:2.1% by
volume
[0615] DVPE=65.0 kPa
[0616] 0.5(RON+MON)=93.0
[0617] Similar results were obtained when other oxygen-containing
compounds (c) and also C.sub.6-C.sub.12 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.
[0618] Moreover, the additive mixture comprising ethanol and the
oxygen-containing compound of this invention other than ethanol
with the ratio of the present invention can be used as an
independent motor fuel for the engines adapted for operation on
ethanol.
EXAMPLE 3
[0619] Example 3 demonstrates the possibility to reduce the dry
vapor pressure equivalent of the ethanol-containing motor fuel for
the cases when gasolines with dry vapor pressure equivalent
according to ASTM D-5191 on a level of 48 kPa (about 7 psi) are
used as a hydrocarbon base.
[0620] 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.
[0621] The source gasolines comprised aliphatic and alicyclic
C.sub.5-C.sub.12 hydrocarbons, including both saturated and
unsaturated ones.
[0622] FIG. 1 shows the behavior 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 behavior.
[0623] The US summer A92 gasoline had the following
specification:
[0624] DVPE=47.8 kPa
[0625] Anti-knock index 0.5(RON+MON)=87.7
[0626] The fuel 3-1 contained US A92 summer gasoline and ethanol
and had the following properties for the different
compositions:
[0627] A92:Ethanol=95:5% by volume
[0628] DVPE=55.9 kPa
[0629] 0.5(RON+MON)=89.0
[0630] A92:Ethanol=90:10% by volume
[0631] DVPE=55.4 kPa
[0632] 0.5(RON+MON)=90.1
[0633] The fuel 3-2 contained US A92 summer gasoline, ethanol, and
the oxygen-containing additives and had the following properties
for the different compositions:
[0634] A92:Ethanol:Isoamyl alcohol=83:8.5:8.5% by volume
[0635] DVPE=47.5 kPa
[0636] 0.5(RON+MON)=89.6
[0637] A92:Ethanol:Isoamyl propionate=82:8:10% by volume
[0638] DVPE=47.0 kPa
[0639] 0.5(RON+MON)=89.9
[0640] A92:Ethanol:2-Ethylhexanol=82:8:10% by volume
[0641] DVPE=47.8 kPa
[0642] 0.5(RON+MON)=89.2
[0643] A92:Ethanol:Tetrahydrofurfuryl alcohol=82:7:10% by
volume
[0644] DVPE=47.8 kPa
[0645] 0.5(RON+MON)=89.3
[0646] A92:Ethanol:Cyclohexanone=82:7:10% by volume
[0647] DVPE=47.7 kPa
[0648] 0.5(RON+MON)=89.1
[0649] A92:Ethanol:Methoxybenzene=80:8.5:11.5% by volume
[0650] DVPE=46.8 kPa
[0651] 0.5(RON+MON)=90.6
[0652] A92:Ethanol:Methoxytoluene=82:8:10% by volume
[0653] DVPE=46.5 kPa
[0654] 0.5(RON+MON)=90.8
[0655] A92:Ethanol:Methylbenzoate=82:8:10% by volume
[0656] DVPE=46.0 kPa
[0657] 0.5(RON+MON)=90.5
[0658] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the US summer
grade gasoline is 7 psi, which corresponds to 48.28 kPa.
[0659] A92:Ethanol:Isoamyl alcohol=83:9:8% by volume
[0660] DVPE=48.2 kPa
[0661] 0.5(RON+MON)=89.8
[0662] A92:Ethanol:Methoxytoluene=84:8:8% by volume
[0663] DVPE=48.2 kPa
[0664] 0.5(RON+MON)=90.5
[0665] A92:Ethanol:Methylbenzoate=85:8:7% by volume
[0666] DVPE=48.2 kPa
[0667] 0.5(RON+MON)=90.1
[0668] The fuel 3-3 contained US A92 summer gasoline (a), ethanol
(b), the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0669] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=75:9.2:0.3:0.1- :15.4% by volume
[0670] The boiling temperature for the naphtha is 100-200.degree.
C.
[0671] DVPE=47.8 kPa
[0672] 0.5(RON+MON)=89.5
[0673] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:m-Isopropyltoluene=75:- 9.2:0.3:0.1:15.4% by volume
[0674] DVPE=47.0 kPa
[0675] 0.5(RON+MON)=90.5
[0676] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Isooctane=75:9.2:0.3:0- .1:15.4% by volume
[0677] DVPE=47.8 kPa
[0678] 0.5(RON+MON)=90.3
[0679] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the US summer
grade gasoline is 7 psi, which corresponds to 48.28 kPa.
[0680] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=76:9.2:0.3:0.1- :14.4% by volume
[0681] The boiling temperature for the naphtha is 100-200.degree.
C.
[0682] DVPE=48.2 kPa
[0683] 0.5(RON+MON)=89.6
[0684] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha:Isooctane=76:9- .2:0.3:0.1:10.4:4% by volume
[0685] The boiling temperature for the naphtha is 100-200.degree.
C.
[0686] DVPE=48.2 kPa
[0687] 0.5(RON+MON)=89.8
[0688] A92:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha:m-Isopropyl toluene=77:9.2:0.3:0.1:10.4:3% by
volume
[0689] The boiling temperature for the naphtha is 100-200.degree.
C.
[0690] DVPE=48.2 kPa
[0691] 0.5(RON+MON)=89.9
[0692] The following fuels demonstrate the possibility of adjusting
the dry vapor pressure equivalent (DVPE) of the ethanol-containing
motor fuel based on US A98 summer gasoline.
[0693] The US A98 gasoline had the following specification:
[0694] DVPE=48.2 kPa
[0695] Anti-knock index 0.5(RON+MON)=92.2
[0696] The comparative fuel 3-4 contained US A98 summer gasoline
and ethanol and had the following properties for the different
compositions:
[0697] A98:Ethanol=95:5% by volume
[0698] DVPE=56.3 kPa
[0699] 0.5(RON+MON)=93.0
[0700] A98:Ethanol=90:10% by volume
[0701] DVPE=55.8 kPa
[0702] 0.5(RON+MON)=93.6
[0703] 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 different compositions:
[0704] A98:Ethanol:Isoamyl alcohol=82.5:9:8.5% by volume
[0705] DVPE=48.2 kPa
[0706] 0.5(RON+MON)=93.3
[0707] A98:Ethanol:Isoamyl alcohol:Isobutyl alcohol=82.5:9:7:1.5%
by volume
[0708] DVPE=48.2 kPa
[0709] 0.5(RON+MON)=93.4
[0710] A98:Ethanol:Tetrahydrofurfuryl alcohol=80:10:10% by
volume
[0711] DVPE=48.0 kPa
[0712] 0.5(RON+MON)=93.7
[0713] The fuel 3-6 contained US A98 summer gasoline (a), ethanol
(b), the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0714] A98:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=75:9.2:0.3:0.1- :15.4% by volume
[0715] The boiling temperature for the naphtha is 100-200.degree.
C.
[0716] DVPE=48.2 kPa
[0717] 0.5(RON+MON)=93.3
[0718] A98:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Isooctane=75:9.2:0.3:0- .1:15.4% by volume
[0719] DVPE=48.2 kPa
[0720] 0.5(RON+MON)=93.9
[0721] A98:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:m-Isopropyltoluene=7:5- .5:9.2:0.3:0.1:14.9% by volume
[0722] DVPE=47.5 kPa
[0723] 0.5(RON+MON)=94.4
[0724] A98:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha:Isooctane=75:9- .2:0.3:0.1:8.4:7% by volume
[0725] The boiling temperature for the naphtha is 100-200.degree.
C.
[0726] DVPE=48.2 kPa
[0727] 0.5(RON+MON)=93.6
[0728] A98:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha:m-Isopropyl toluene=75:9.2:0.3:0.1:10.4 5% by
volume
[0729] The boiling temperature for the naphtha is 100-200.degree.
C.
[0730] DVPE=48.0 kPa
[0731] 0.5(RON+MON)=93.7
[0732] A98:Ethanol:Isoamyl alcohol:Isobutyl alcohol:Naphtha
Alkylate=75:9.2:0.3 0.1:7.9:7.5% by volume
[0733] The boiling temperature for the naphtha is 100-200.degree.
C.
[0734] The boiling temperature for the alkylate is 100-130.degree.
C.
[0735] DVPE=48.2 kPa
[0736] 0.5(RON+MON)=93.6
[0737] The following fuels demonstrated the possibility of
adjusting the dry vapor pressure equivalent (DVPE) of the
ethanol-containing motor fuel based on US summer A95 gasoline.
[0738] The US summer A95 gasoline had the following
specification:
[0739] DVPE=47.0 kPa
[0740] Anti-knock index 0.5(RON+MON)=90.9
[0741] 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 liter engine
(No. LG4F20-87) developing 83 kW at 90 revolutions/second and a
torque of 185 Nm at 46 revolutions/second.
[0742] The testing performed as above demonstrated for the US
summer A95 gasoline the following results:
10 CO (carbon monoxide) 2.406 g/km; HC (hydrocarbons) 0.356 g/km;
NO.sub.x (nitrogen oxides) 0.278 g/km; CO.sub.2 (carbon dioxide)
232.6 g/km; NMHC* 0.258 g/km; Fuel consumption, F.sub.c (1/100 km)
9.93 *Non-methane hydrocarbons.
[0743] The comparative fuel 3-7 contained US A95 summer gasoline
and ethanol and had the following properties for the different
compositions:
[0744] A95:Ethanol=95:5% by volume
[0745] DVPE=55.3 kPa
[0746] 0.5(RON+MON)=91.5
[0747] A95:Ethanol=90:10% by volume
[0748] DVPE=54.8 kPa
[0749] 0.5(RON+MON)=92.0
[0750] The testing of the reference gasoline-alcohol mixture (RFM
3) comprising 90% by volume of US A95 summer grade gasoline and 10%
by volume of ethanol performed on a 1987 VOLVO 240 DL with a B230F,
4-cylinder, 2.32 liter engine (No. LG4F20-87) in accordance with
the standard test method EU 2000 NEDC EC 98/69 demonstrated the
following results, as compared to summer US A95 gasoline:
11 CO -12.5%; HC -4.8%; NO.sub.x +2.3%; CO.sub.2 +3.7%; NMHC*
-4.0%; Fuel consumption, F.sub.c (1/100 km) +3.1% -represents a
reduction in emission, while +represents an increase in
emission.
[0751] The fuel 3-8 contained US A95 summer gasoline, ethanol and
the oxygen-containing additives, and had the following properties
for the different compositions:
[0752] A95:Ethanol:Isoamyl alcohol=83:8.5:8.5% by volume
[0753] DVPE=47.0 kPa
[0754] 0.5(RON+MON)=91.7
[0755] A95:Ethanol:n-Amyl acetate=80:10:10% by volume
[0756] DVPE=47.0 kPa
[0757] 0.5(RON+MON)=91.8
[0758] A95:Ethanol:Cyclohexylacetate=80:10:10% by volume
[0759] DVPE=46.7 kPa
[0760] 0.5(RON+MON)=92.0
[0761] A95:Ethanol:Tetramethyltetrahydrofuran=80:12:8% by
volume
[0762] DVPE=47.0 kPa
[0763] 0.5(RON+MON)=92.6
[0764] A95:Ethanol:Methyltetrahydropyran=80:15:5% by volume
[0765] DVPE=46.8 kPa
[0766] 0.5(RON+MON)=92.5
[0767] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the US summer
grade gasoline is 7 psi, which corresponds to 48.28 kPa.
[0768] A95:Ethanol:Isoamyl alcohol=84:8.5:7.5% by volume
[0769] DVPE=48.2 kPa
[0770] 0.5(RON+MON)=91.7
[0771] A95:Ethanol:Phenylacetate=82.5:10:7.5% by volume
[0772] DVPE=48.2 kPa
[0773] 0.5(RON+MON)=92.3
[0774] A95:Ethanol:Tetramethyltetrahydrofuran=81:10:9% by
volume
[0775] DVPE=48.2 kPa
[0776] 0.5(RON+MON)=92.2
[0777] The fuel 3-9 contained US A95 summer gasoline (a), ethanol
(b), the oxygen-containing additives (c), and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0778] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=75:9.2:0.3:0.1- :15.4% by volume
[0779] The boiling temperature for the naphtha is 100-200.degree.
C.
[0780] DVPE=47.0 kPa
[0781] 0.5(RON+MON)=91.6
[0782] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Isooctane=75:9.2:0.3:0- .1:15.4% by volume
[0783] DVPE=47.0 kPa
[0784] 0.5(RON+MON)=92.2
[0785] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:m-Isopropyltoluene=75:- 9.2:0.3:0.1:15.4% by volume
[0786] DVPE=46.8 kPa
[0787] 0.5(RON+MON)=93.0
[0788] A95:Ethanol:Tetrahydrofurfuryl
alcohol:Cyclooctatetraene=80:9.5:0.5- :10% by volume
[0789] DVPE=46.6 kPa
[0790] 0.5(RON+MON)=92.5
[0791]
A95:Ethanol:4-Methyl-4-oxytetrahydropyran:Allocymene=80:9.5:0.5:10%
by volume
[0792] DVPE=46.7 kPa
[0793] 0.5(RON+MON)=92.1
[0794] 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 get it in
compliance with the requirements of the regulations in force
towards corresponding gasoline. The DVPE level for the US summer
grade gasoline is 7 psi, which corresponds to 48.28 kPa.
[0795] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=76.5:9.2:0.3:0- .1:13.9% by volume
[0796] The boiling temperature for the naphtha is 100-200.degree.
C.
[0797] DVPE=48.2 kPa
[0798] 0.5(RON+MON)=91.7
[0799] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha:Isooctane=76.5- :9.2:0.3:0.1:7.0:6.9% by volume
[0800] The boiling temperature for the naphtha is 100-200.degree.
C.
[0801] DVPE=48.2 kPa
[0802] 0.5(RON+MON)=92.2
[0803] A95:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:m-Isopropyltoluene=77:- 9.2:0.3:0.1:13.4% by volume
[0804] DVPE=48.2 kPa
[0805] 0.5(RON+MON)=92.9
[0806] 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.degree. C.,
and 3% by volume of isopropyltoluene. Formulation 3-10 was tested
to demonstrate how the invention enables the production of
ethanol-containing gasoline entirely meeting the requirements of
the standards in force, firstly towards level of the DVPE and also
towards other parameters. At the same time this gasoline secures
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:
12 density at 15.degree. C., according to 774.9 kg/m.sup.3; ASTM
D-4052 initial boiling point, according 36.1.degree. C.; to ASTM
D-86 vaporizable portion - 70.degree. C. 33.6% by volume;
vaporizable portion - 100.degree. C. 50.8% by volume; vaporizable
portion - 150.degree. C. 86.1% by volume; vaporizable portion -
190.degree. C. 97.0% by volume; final boiling point 204.8.degree.
C.; evaporation residue 1.5% by volume; loss by evaporation 1.5% by
volume; oxygen content, according to 3.37% w/w; ASTM D-4815
acidity, according to ASTM D- 0.007; 1613 weight % HAc pH,
according to ASTM D-1287 7.58; sulfur content, according to 47
mg/kg; ASTM D-5453 gum content, according to ASTM 2.8 mg/100 ml;
D-381 water content, according to ASTM 0.02% w/w; D-6304 aromatics,
according to SS 31.2% by 155120, including benzene volume; benzene
alone, according to EN 0.7% by volume; 238 DVPE, according to ASTM
D-5191 48.0 kPa; anti-knock index 0.5 (RON + MON), 92.2 according
to ASTM D-2699-86 and ASTM D-2700-86
[0807] The motor fuel Formulation 3-10 was tested on a 1987 VOLVO
240 DL with a B230F, 4-cylinder, 2.32 liter 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:
13 CO -15.1% HC -5.6%; NO.sub.x +0.5%; CO.sub.2 unchanged; NMHC
-4.5%; Fuel consumption, F.sub.c (1/100 km) unchanged.
[0808] Similar results were obtained when the other
oxygen-containing compounds substituted the tested
oxygen-containing compounds.
[0809] 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.degree.
C. All the above formulations were prepared without the use of any
mixing devices.
[0810] It was established that there is a possibility of employing
the additive mixture comprising ethanol and oxygen-containing
compounds other than ethanol also for adjustment of the vapor
pressure of the ethanol-containing motor fuels used in standard
internal combustion spark ignition engines based on summer grade
gasolines meeting US standards. Adding C.sub.8-C.sub.12
hydrocarbons to the composition of the additive mixture increased
the efficiency of the vapor pressure reducing impact of the
additive on the excess vapor pressure caused by presence in the
gasoline of ethanol.
[0811] The additive mixture comprising 60% by volume of ethanol,
32% by volume of isoamyl alcohol and 8% by volume of isobutyl
alcohol was in different proportions mixed with US summer grade
gasolines having dry vapor pressure equivalent (DVPE) not higher
than 7 psi, which corresponds 48.28 kPa.
[0812] The obtained compositions had the following properties:
[0813] A92:Ethanol:Isoamyl alcohol:Isobutanol=87.5:7.5:4:1% by
volume
[0814] DVPE=51.7 kPa
[0815] 0.5(RON+MON)=89.7
[0816] A95:Ethanol:Isoamyl alcohol:Isobutanol=85:9:4.8:1.2% by
volume
[0817] DVPE=51.0 kPa
[0818] 0.5(RON+MON)=91.8
[0819] A98:Ethanol:Isoamyl alcohol:Isobutanol=80:12:6.4:1.6% by
volume
[0820] DVPE=52.0 kPa
[0821] 0.5(RON+MON)=93.5
[0822] The foregoing examples demonstrate the possibility of
partially lowering the excess vapor pressure, by about 50% of the
excess vapor pressure of gasoline induced by presence of ethanol in
the mixture.
[0823] 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 vapor pressure
equivalent (DVPE) not higher than 7 psi, which corresponds to 48.28
kPa. The obtained compositions had the following properties:
[0824] A92:Ethanol:Methylisobutyl ketone=85:7.5:7.5% by volume
[0825] DVPE=49.4 kPa
[0826] 0.5(RON+MON)=90.0
[0827] A95:Ethanol:Methylisobutyl ketone=84:8:8% by volume
[0828] DVPE=48.6 kPa
[0829] 0.5(RON+MON)=91.7
[0830] A98:Ethanol:Methylisobutyl ketone=82:9:9% by volume
[0831] DVPE=49.7 kPa
[0832] 0.5(RON+MON)=93.9
[0833] The foregoing examples demonstrate the possibility of
partial lowering of the excess vapor pressure by about 80% of the
excess vapor pressure of gasoline induced by presence of ethanol in
the mixture.
[0834] FIG. 2 shows the behavior of the dry vapor 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.degree. C., and 20% of
isopropyl toluene.
[0835] FIG. 2 demonstrates that employment of this additive mixture
in formulation of ethanol-containing gasoline enables the reduction
that is greater than 100% of the excess vapor pressure induced by
presence of ethanol.
[0836] 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.degree. C. and 20% by volume of isopropyltoluene.
[0837] Similar results were obtained when other oxygen-containing
compounds and C.sub.6-C.sub.12 hydrocarbons of this invention were
used in the proportion established by this invention to formulate
the additive mixture, which was then used for preparation of the
ethanol-containing gasolines. These gasolines entirely meet the
requirements towards the motor fuels used in standard internal
combustion spark ignition engines.
[0838] Moreover, the additive mixture comprising ethanol, the
oxygen-containing compound other than ethanol, and C.sub.6-C.sub.12
hydrocarbons in the proportion and composition of the present
invention, can be used as an independent motor fuel for the engines
adopted for operation on ethanol.
EXAMPLE 4
[0839] Example 4 demonstrates the possibility to reduce the dry
vapor 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 vapor pressure equivalent according to ASTM
D-5191 on a level of 110 kPa (about 16 psi).
[0840] 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 (GC) purchased in Russia from
GAZPROM were used.
[0841] 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).
[0842] 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 obtained
hydrocarbon component (HCC) was then allowed to stand for 24 hours.
The resulting gasoline contained aliphatic and alicyclic
C.sub.3-C.sub.12 hydrocarbons, including saturated and unsaturated
ones.
[0843] FIG. 1 demonstrates the behavior 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
behavior.
[0844] Gasoline comprising 85% by volume of winter gasoline A92 and
15% by volume of gas condensate (GC) had the following
properties:
[0845] DVPE=110.0 kPa
[0846] Anti-knock index 0.5(RON+MON)=87.9
[0847] The comparative fuel 4-1 contained A92 winter gasoline, gas
condensate (GC) and ethanol and had the following properties for
the different compositions:
[0848] A92:GC:Ethanol=80.75:14.25:5% by volume
[0849] DVPE=115.5 kPa
[0850] 0.5(RON+MON)=89.4
[0851] A92:GC:Ethanol=76.5:13.5:10% by volume
[0852] DVPE=115.0 kPa
[0853] 0.5(RON+MON)=90.6
[0854] 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 different compositions:
[0855] A92:GC:Ethanol:Isoamyl alcohol=74:13:6.5:6.5% by volume
[0856] DVPE=109.8 kPa
[0857] 0.5(RON+MON)=90.35
[0858] A92:GC:Ethanol:2,5 Dimethyltetrahydrofuran=68:12:10:10% by
volume
[0859] DVPE=110.0 kPa
[0860] 0.5(RON+MON)=90.75
[0861] A92:GC:Ethanol:Propanol=68:12:12:8% by volume
[0862] DVPE=109.5 kPa
[0863] 0.5(RON+MON)=90.0
[0864] A92:GC:Ethanol:Diisopropylcarbinol=72:13:7.5:7.5% by
volume
[0865] DVPE=109.0 kPa
[0866] 0.5(RON+MON)=90.3
[0867] A92:GC:Ethanol:Acetophenone=72:13:9:6% by volume
[0868] DVPE=110.0 kPa
[0869] 0.5(RON+MON)=90.8
[0870] A92:GC:Ethanol:Isobutylpropionate=75:13:5:7% by volume
[0871] DVPE=109.2 kPa
[0872] 0.5(RON+MON)=90.0
[0873] The fuel 4-3 contained winter A92 gasoline, gas condensate
(GC), ethanol, the oxygen-containing additive and C.sub.6-C.sub.12
hydrocarbons and had the following properties for the different
compositions:
[0874] A92:GC:Ethanol:Isobutanol:Isopropylbenzene=68:12:9.5:0.5:10%
by volume
[0875] DVPE=108.5 kPa
[0876] 0.5(RON+MON)=91.7
[0877] A92:GC:Ethanol:Tert-butyl ethyl
ether:Naphtha=68:12:9.5:0.5:10% by volume
[0878] The boiling temperature for the naphtha is 100-200.degree.
C.
[0879] DVPE=108.5 kPa
[0880] 0.5(RON+MON)=90.6
[0881] A92:GC:Ethanol:Isoamyl methyl
ether:Toluene=68:12:9.5:0.5:10% by volume
[0882] DVPE=107.5 kPa
[0883] 0.5(RON+MON)=91.6
[0884] 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 standard gasoline. The
DVPE for the standard A92 winter gasoline is 90 kPa.
[0885] A92:GC:Ethanol:Isoamyl
alcohol:Naphtha:Alkylate=55:10:9.5:0.5:12.5:- 12.5% by volume
[0886] The boiling temperature for the naphtha is 100-200.degree.
C.
[0887] The boiling temperature for the alkylate is 100-130.degree.
C.
[0888] DVPE=90.0 kPa
[0889] 0.5(RON+MON)=90.6
[0890] A92:GC:Ethanol:Isoamyl
alcohol:Naphtha:Ethylbenzene=55:10:9.5:0.5:1- 5:10% by volume
[0891] The boiling temperature for the naphtha is 100-200.degree.
C.
[0892] DVPE=89.8 kPa
[0893] 0.5(RON+MON)=90.9
[0894] A92:GC:Ethanol:Isoamyl
alcohol:Naphtha:Isopropyltoluene=55:10:9.5:0- .5:20:5% by
volume
[0895] The boiling temperature for the naphtha is 100-200.degree.
C.
[0896] DVPE=90.0 kPa
[0897] 0.5(RON+MON)=90.6
[0898] The following compositions demonstrate the possibility of
adjustment of the dry vapor pressure equivalent (DVPE) of the
ethanol-containing fuel mixtures based on about 85% by volume of
winter A98 gasoline and about 15% by volume of gas condensate.
[0899] The gasoline comprising 85% by volume of winter A98 gasoline
and 15% by volume of gas condensate (GC) had the following
specification:
[0900] DVPE=109.8 kPa
[0901] Anti-knock index 0.5(RON+MON)=92.0
[0902] The comparative fuel 4-4 contained A98 winter gasoline, gas
condensate (GC) and ethanol and had the following properties for
the different compositions:
[0903] A98:GC:Ethanol=80.75:14.25:5% by volume
[0904] DVPE=115.3 kPa
[0905] 0.5(RON+MON)=93.1
[0906] A98:GC:Ethanol=76.5:13.5:10% by volume
[0907] DVPE=114.8 kPa
[0908] 0.5(RON+MON)=94.0
[0909] The inventive fuel 4-5 contained A98 winter gasoline, gas
condensate (GC) and the oxygen-containing additives and had the
following properties for the different compositions:
[0910] A98:GC:Ethanol:Isoamyl alcohol=74:13:6.5:6.5% by volume
[0911] DVPE=109.6 kPa
[0912] 0.5(RON+MON)=93.3
[0913] A98:GC:Ethanol:Methoxybenzene=72:13:7.5:7.5% by volume
[0914] DVPE=110.0 kPa
[0915] 0.5(RON+MON)=94.0
[0916] A98:GC:Ethanol:3,3,5 Trimethylcyclohexanone=72:13:7.5:7.5%
by volume
[0917] DVPE=109.8 kPa
[0918] 0.5(RON+MON)=93.3
[0919] The fuel 4-6 contained A98 winter gasoline, gas condensate,
ethanol, the oxygen-containing additives, and C.sub.6-C.sub.12
hydrocarbons (d) and had the following properties for the different
compositions:
[0920] A98:GC:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=68:12:9.2:0- .6:0.2:10% by volume
[0921] The boiling temperature for the naphtha is 100-200.degree.
C.
[0922] DVPE=107.4 kPa
[0923] 0.5(RON+MON)=93.8
[0924] A98:GC:Ethanol:Ethylisobutyl ether:Myrcene=72:13:9.5:0.5:5%
by volume
[0925] DVPE=110.0 kPa
[0926] 0.5(RON+MON)=93.6
[0927] A98:GC:Ethanol:Isobutanol:Isooctane=68:12:5:5:10% by
volume
[0928] DVPE=102.5 kPa
[0929] 0.5(RON+MON)=93.5
[0930] The motor fuel compositions below demonstrate that the
invention enables the reduction of the excess DVPE of non-standard
gasoline to the level of DVPE of the corresponding standard
gasoline. The DVPE for the standard winter A98 gasoline is 90.0
kPa.
[0931] A92:GC:Ethanol:Isoamyl
alcohol:Naphtha:Alkylate=55:10:9.5:0.5:12.5 12.5% by volume
[0932] The boiling temperature for the naphtha is 100-200.degree.
C.
[0933] The boiling temperature for the alkylate is 100-130.degree.
C.
[0934] DVPE=89.8 kPa
[0935] 0.5(RON+MON)=94.0
[0936] A92:GC:Ethanol:Isoamyl
alcohol:Naphtha:Isopropylbenzene=55:10:9.5:0- .5:15:10% by
volume
[0937] The boiling temperature for the naphtha is 100-200.degree.
C.
[0938] DVPE=89.6 kPa
[0939] 0.5(RON+MON)=94.2
[0940]
A92:GC:Ethanol:Isobutanol:Naphtha:Isopropyltoluene=55:10:5:5:20:5%
by volume
[0941] The boiling temperature for the naphtha is 100-200.degree.
C.
[0942] DVPE=88.5 kPa
[0943] 0.5(RON+MON)=94.1
[0944] The following compositions demonstrate the possibility of
adjustment of the dry vapor 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 condensate.
[0945] The gasoline comprising 85% by volume of winter A98 gasoline
and 15% by volume of gas condensate (GC) had the following
specification:
[0946] DVPE=109.5 kPa
[0947] Anti-knock index 0.5(RON+MON)=90.2
[0948] 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:
14 CO 2.033 g/km; HC 0.279 g/km; NO.sub.x 0.279 g/km; CO.sub.2
229.5 g/km; NMHC 0.255 g/km; Fuel consumption, F.sub.c (1/100 km)
9.89
[0949] The fuel 4-7 contained A95 winter gasoline, gas condensate
(GC) and ethanol and had the following properties for the different
compositions:
[0950] A95:GC:Ethanol=80.75:14.25:5% by volume
[0951] DVPE=115.0 kPa
[0952] 0.5(RON+MON)=91.7
[0953] A95:GC:Ethanol=76.5:13.5 10% by volume
[0954] DVPE=114.5 kPa
[0955] 0.5(RON+MON)=92.5
[0956] The reference fuel mixture (RFM 4) 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):
15 CO -6.98% HC -7.3%; NO.sub.x +12.1%; CO.sub.2 +1.1%; NMHC -5.3%;
Fuel consumption, F.sub.c (1/100 km) +2.62%
[0957] 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 different compositions:
[0958] A95:GC:Ethanol:Isoamyl alcohol=74:13:6.5:6.5% by volume
[0959] DVPE=109.1 kPa
[0960] 0.5(RON+MON)=92.0
[0961] A95:GC:Ethanol:Phenol=72:13:8:7% by volume
[0962] DVPE=107.5 kPa
[0963] 0.5(RON+MON)=92.6
[0964] A95:GC:Ethanol:Phenyl acetate=68:12:10:10% by volume
[0965] DVPE=106.0 kPa
[0966] 0.5(RON+MON)=92.8
[0967] A95:GC:Ethanol:3-Hydroxy-2-butanone=68:12:10:10% by
volume
[0968] DVPE=108.5 kPa
[0969] 0.5(RON+MON)=91.6
[0970] A95:GC:Ethanol:Tert-butylacetoacetate=68:12:10:10% by
volume
[0971] DVPE=108.0 kPa
[0972] 5.5(RON+MON)=92.2
[0973] A95:GC:Ethanol:3,3,5-Trimethylcyclohexanone=71:12:9:8% by
volume
[0974] DVPE=108.5 kPa
[0975] 0.5(RON+MON)=91.6
[0976] The fuel 4-9 contained A95 winter gasoline, gas condensate
(GC), ethanol, the oxygen-containing additives, and
C.sub.6-C.sub.12 hydrocarbons (d) and had the following properties
for the different compositions:
[0977] A95:GC:Ethanol:Isoamyl alcohol:Isobutyl
alcohol:Naphtha=68:12:9.2:0- .6:0.2:10% by volume
[0978] The boiling temperature for the naphtha is 100-200.degree.
C.
[0979] DVPE=107.0 kPa
[0980] 0.5(RON+MON)=92.1
[0981] A95:GC:Ethanol:Isobutanol:Cyclooctatetraene=72:13:9.5:0.5:5%
by volume
[0982] DVPE=108.5 kPa
[0983] 0.5(RON+MON)=92.6
[0984] The motor fuel compositions below demonstrate that the
invention enables the reduction of the excess vapor pressure
equivalent (DVPE) of the non-standard gasoline to the level of the
corresponding standard gasoline.
[0985] The DVPE of the standard winter gasoline A95 is 90.0
kPa.
[0986] A95:GC:Ethanol:Isoamyl
alcohol:Isobutanol:Naphtha:Alkylate=55:10:9.- 2:0.6:0.2:12.5:12.5%
by volume
[0987] The boiling temperature for the naphtha is 100-200.degree.
C.
[0988] The boiling temperature for the alkylate is 100-130.degree.
C.
[0989] DVPE=89.5 kPa
[0990] 0.5(RON+MON)=92.4
[0991] A95:GC:Ethanol:Isoamyl
alcohol:Naphtha:Tertbutylxylene=55:10:9.5:0.- 5:20:5% by volume
[0992] The boiling temperature for the naphtha is 100-200.degree.
C.
[0993] DVPE=89.8 kPa
[0994] 0.5(RON+MON)=92.5
[0995]
A95:GC:Ethanol:Isobutanol:Naphtha:Isopropylbenzene=55:10:5:5:20:5%
by volume
[0996] The boiling temperature for the naphtha is 100-200.degree.
C.
[0997] DVPE=89.9 kPa
[0998] 0.5(RON+MON)=92.2
[0999] The motor fuel 4-10 contained 55% by volume of A95 winter
gasoline, 10% by volume 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.degree. C. and 5% by volume of
isopropyltoluene. Formulation 4-10 was tested to demonstrate how
the invention enables the formulation of the ethanol-containing
gasoline entirely meeting requirements of the standards in force,
firstly in respect of dry vapor pressure equivalent limit, and also
for the other parameters of the fuel, even when the source
hydrocarbon component (HCC) has a DVPE considerably higher than the
requirements of the standards. At the same time this
ethanol-containing gasoline decreases the level of toxic emissions
in the exhaust and decreases the fuel consumption in comparison
with the above-described mixture RFM 4. The formulation 4-10 had
the following specific properties:
16 density at 15.degree. C., according to ASTM D- 698.6 kg/m.sup.3;
4052 initial boiling point, according to 20.5.degree. C.; ASTM D-86
vaporizable portion - 70.degree. C. 47.0% by volume; vaporizable
portion - 100.degree. C. 65.2% by volume; vaporizable portion -
150.degree. C. 92.4% by volume; vaporizable portion - 180.degree.
C. 97.3% by volume; final boiling point 189.9.degree. C.;
evaporation residue 0.5% by volume; loss by evaporation 1.1% by
volume; oxygen content, according to ASTM D- 3.2% w/w; 4815
acidity, according to ASTM D-1613 0.001; weight % HAc pH, according
to ASTM D-1287 7.0; sulfur content, according to ASTM D- 18 mg/kg;
5453 gum content, according to ASTM D-381 2 mg/100 ml; water
content, according to ASTM D-6304 0.01% w/w; aromatics, according
to SS 155120, 30.9% by including benzene 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), 92.3 according to ASTM
D 2699-86 and ASTM D 2700-86
[1000] 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:
17 CO -14.0% HC -8.6%; NO.sub.x unchanged; CO.sub.2 +1.0%; NMHC
-6.7%; Fuel consumption, F.sub.c (1/100 km) +2.0%
[1001] Similar results are obtained when other oxygen-containing
additives of the invention are substituted for the
oxygen-containing additives of the examples 4-1 to 4-10.
[1002] To prepare all the above fuel formulations 4-1 to 4-10 of
this motor fuel composition, the hydrocarbon component (HCC), which
is a mixture of winter gasoline and gas condensate (GC), was
initially mixed with ethanol, to which mixture then was added the
corresponding oxygen-containing additive and C.sub.6-C.sub.12
hydrocarbons. The motor fuel composition obtained was then allowed
to stand before testing between 1 and 24 hours at a temperature not
lower than -35.degree. C. All the above formulations were prepared
without the use of any mixing devices.
[1003] The inventive fuel formulations demonstrated the possibility
to adjust the vapor pressure of the ethanol-containing motor fuels
for the standard internal combustion spark ignition engines based
on non-standard gasolines having a high vapor pressure.
[1004] FIG. 2 shows the behavior of the dry vapor 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.
[1005] FIG. 2 demonstrates that employment of this additive mixture
comprising ethanol and the oxygen-containing additive other than
ethanol enables the attainment of ethanol-containing gasolines, the
vapor pressure of which does not exceed the vapor pressure of the
source hydrocarbon component (HCC).
[1006] 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.
[1007] Similar results were obtained when other oxygen-containing
compounds and C.sub.6-C.sub.12 hydrocarbons of this invention were
used in the proportion of the invention to formulate the additive
mixture, which was then used for preparation of the
ethanol-containing gasolines.
[1008] These gasoline mixtures of the invention have a vapor
pressure equivalent (DVPE) which does not exceed the DVPE of the
source hydrocarbon component (HCC). At the same time it is possible
to add the oxygen-containing additive only in the amount sufficient
to obtain the ethanol-containing gasoline entirely in compliance
with requirements towards the motor fuels used in the standard
internal combustion spark ignition engines.
EXAMPLE 5
[1009] Example 5 demonstrates the possibility to reduce the dry
vapor pressure equivalent of the ethanol-containing motor fuel for
the cases when the hydrocarbon base of the fuel is a reformulated
gasoline with dry vapor pressure equivalent according to ASTM
D-5191 on a level of 27.5 kPa (about 4 psi).
[1010] To prepare the mixtures of this composition lead-free
reformulated gasoline purchased in Sweden from PREEM and in Russia
from LUKOIL, and the Petroleum benzine purchased from MERK in
Germany were used.
[1011] 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).
[1012] The source gasolines comprised aliphatic and alicyclic
C.sub.6-C.sub.12 hydrocarbons, including saturated and
unsaturated.
[1013] FIG. 1 demonstrates the behavior of the DVPE of the
ethanol-containing motor fuel based on reformulated gasoline A92
and Petroleum benzine. Similar behavior was observed for the
ethanol-containing motor fuel based on reformulated A95 and A98
gasoline, and Petroleum benzine.
[1014] It should be pointed out that addition of ethanol to the
reformulated gasoline induces a higher vapor pressure increase
compared to the addition of ethanol to the standard gasoline.
[1015] Gasoline comprising 80% by volume of reformulated gasoline
A92 and 20% by volume of Petroleum benzine (PB) had the following
properties:
[1016] DVPE=27.5 kPa
[1017] Anti-knock index 0.5(RON+MON)=85.5
[1018] The comparative fuel 5-1 contained A92 reformulated
gasoline, Petroleum benzine (PB) and ethanol and had the following
properties for the different compositions:
[1019] A92:PB:Ethanol=76:19:5% by volume
[1020] DVPE=36.5 kPa
[1021] 0.5(RON+MON)=89.0
[1022] A92:PB:Ethanol=72:18:10% by volume
[1023] DVPE=36.0 kPa
[1024] 0.5(RON+MON)=90.7
[1025] 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 different
compositions:
[1026] A92:PB:Ethanol:Isoamyl alcohol=64:16:10:10% by volume
[1027] DVPE=27.0 kPa
[1028] 0.5(RON+MON)=90.5
[1029] A92:PB:Ethanol:Diisobutyl ether=64:16:10:10% by volume
[1030] DVPE=27.5 kPa
[1031] 0.5(RON+MON)=90.8
[1032] A92:PB:Ethanol:n-Butanol=64:16:10:10% by volume
[1033] DVPE=27.5 kPa
[1034] 0.5(RON+MON)=90.1
[1035] A92:PB:Ethanol:2,4,4-Trimethyl-1-pentanol=64:16:10:10% by
volume
[1036] DVPE=25.0 kPa
[1037] 0.5(RON+MON)=91.8
[1038] The fuel 5-3 contained reformulated A92 gasoline, Petroleum
benzine (PB), ethanol, the oxygen-containing additives and also
C.sub.8-C.sub.12 hydrocarbons and had the following properties for
the different compositions:
[1039] A92:PB:Ethanol:Isoamyl alcohol:Naphtha=60:15:9.2:0.8:15% by
volume
[1040] The boiling temperature for the naphtha is 140-200.degree.
C.
[1041] DVPE=27.5 kPa
[1042] 0.5(RON+MON)=89.3
[1043]
A92:PB:Ethanol:n-Butanol:Naphtha:Xylene=60:15:9.2:0.8:7.5:7.5% by
volume
[1044] The boiling temperature for the naphtha is 140-200.degree.
C.
[1045] DVPE=27.5 kPa
[1046] 0.5(RON+MON)=91.2
[1047] A92:PB:Ethanol:Tetrahydrofurfuryl
alcohol:Isopropylbenzene=60:15:9:- 1:15% by volume
[1048] DVPE=27.5 kPa
[1049] 0.5(RON+MON)=91.3
[1050] The fuel compositions below demonstrate the possibility to
adjust the dry vapor pressure equivalent of the ethanol-containing
gasolines based on reformulated A98 gasoline and Petroleum benzine
(PB).
[1051] The motor fuel comprising 80% by volume of reformulated
gasoline A98 and 20% by volume of Petroleum benzine (PB) had the
following properties:
[1052] DVPE=27.3 kPa
[1053] Anti-knock index 0.5(RON+MON)=88.0
[1054] The comparison fuel 5-4 contained A98 reformulated gasoline,
Petroleum benzine (PB) and ethanol and had the following properties
for the different compositions:
[1055] A98:PB:Ethanol=76:19:5% by volume
[1056] DVPE=36.3 kPa
[1057] 0.5(RON+MON)=91.0
[1058] A98:PB:Ethanol=72:18:10% by volume
[1059] DVPE=35.8 kPa
[1060] 0.5(RON+MON)=92.5
[1061] 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 different
compositions:
[1062] A98:PB:Ethanol:Isoamyl alcohol=64:16:10:10% by volume
[1063] DVPE=26.9 kPa
[1064] 0.5(RON+MON)=92.0
[1065] A98:PB:Ethanol:n-Amyl alcohol=64:16:10:10% by volume
[1066] DVPE=26.5 kPa
[1067] 0.5(RON+MON)=91.2
[1068] A98:PB:Ethanol:Linalool=68:17:9:6% by volume
[1069] DVPE=27.1 kPa
[1070] 0.5(RON+MON)=92.6
[1071] A98:PB:Ethanol:3,6-Dimethyl-3-octanol=68:17:9:6% by
volume
[1072] DVPE=27.0 kPa
[1073] 0.5(RON+MON)=92.5
[1074] The fuel 5-6 contained A98 reformulated gasoline, Petroleum
benzine (PB), ethanol, the oxygen-containing additives, and
C.sub.8-C.sub.12 hydrocarbons (d) and had the following properties
for the different compositions:
[1075] A98:PB:Ethanol:Isoamyl alcohol:Naphtha=60:15:9.2:0.8:15% by
volume
[1076] The boiling temperature for the naphtha is 140-200.degree.
C.
[1077] DVPE=27.0 kPa
[1078] 0.5(RON+MON)=91.7
[1079] A98:PB:Ethanol:Linalool:Allocymene=60:15:9:1:15% by
volume
[1080] DVPE=26.0 kPa
[1081] 0.5(RON+MON)=93.0
[1082] A98:PB:Ethanol:Methylcyclohexanol:Limonene=60:15:9.5:1:14.5%
by volume
[1083] DVPE=25.4 kPa
[1084] 0.5(RON+MON)=93.2
[1085] The motor fuel compositions below demonstrate the
possibility to adjust the dry vapor 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 Petroleum
benzine (PB). Gasoline comprising 80% by volume of the reformulated
A95 gasoline and 20% by volume of the Petroleum benzine (PB) had
the following properties:
[1086] DVPE=27.6 kPa
[1087] Anti-knock index 0.5(RON+MON)=86.3
[1088] 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 liter engine (No. LG4F20-87) in
accordance with test method EU 2000 NEDC EC 98/69 and gave the
following results:
18 CO 2.631 g/km; HC 0.348 g/km; NO.sub.x 0.313 g/km; CO.sub.2
235.1 g/km; NMHC 0.308 g/km; Fuel consumption, F.sub.c (1/100 km)
10.68
[1089] The fuel 5-7 contained A95 reformulated gasoline, Petroleum
benzine (PB) and ethanol and had the following properties for the
different compositions:
[1090] A95:PB:Ethanol=76:19:5% by volume
[1091] DVPE=36.6 kPa
[1092] 0.5(RON+MON)=90.2
[1093] A95:PB:Ethanol=72:18:10% by volume
[1094] DVPE=36.1 kPa
[1095] 0.5(RON+MON)=91.7
[1096] The reference fuel mixture (RFM 5) 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 liter engine (No. LG4F20-87) in
accordance with test method EU 2000 NEDC EC 98/69 as above and gave
the following results in comparison (+) or (-) % with the results
for the gasoline comprising 80% by volume of reformulated gasoline
A95 and 20% by volume of Petroleum benzine (GC):
19 CO -4.8% HC -1.3%; NO.sub.x +26.3%; CO.sub.2 +4.4%; NMHC -0.6%;
Fuel consumption, F.sub.c (1/100 km) +5.7%
[1097] The fuel 5-8 contained A95 reformulated gasoline, Petroleum
benzine (PB), ethanol and the oxygen-containing additives and had
the following properties for the different compositions:
[1098] A95:PB:Ethanol:Isoamyl alcohol=64:16:10:10% by volume
[1099] DVPE=27.1 kPa
[1100] 0.5(RON+MON)=92.0
[1101] A95:PB:Ethanol:2,6-Dimethyl-4-heptanol=64:16:10:10% by
volume
[1102] DVPE=27.0 kPa
[1103] 0.5(RON+MON)=92.4
[1104] A95:PB:Ethanol:Tetrahydrofurfuryl acetate=60:15:15:10% by
volume
[1105] DVPE=25.6 kPa
[1106] 0.5(RON+MON)=93.0
[1107] The fuel 5-9 contained A95 reformulated gasoline, Petroleum
benzine (PB), ethanol, the oxygen-containing additives, and
C.sub.8-C.sub.12 hydrocarbons and had the following properties for
the different compositions:
[1108] A95:PB:Ethanol:Isoamyl alcohol:Naphtha=60:15:9.2:0.8:15% by
volume
[1109] The boiling temperature for the naphtha is 140-200.degree.
C.
[1110] DVPE=27.1 kPa
[1111] 0.5(RON+MON)=91.4
[1112] A95:PB:Ethanol:Tetrahydrofurfuryl
alcohol:Tertbutylcyclohexane=60:1- 5:9.2:0.8:15% by volume
[1113] DVPE=26.5 kPa
[1114] 0.5(RON+MON)=90.7
[1115]
A95:PB:Ethanol:4-Methyl-4-hydroxytetrahydropyran:Isopropyltoluene=6-
0:15:9.2:0.8:15% by volume
[1116] DVPE=26.1 kPa
[1117] 0.5(RON+MON)=92.0
[1118] 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 2,5-Dimethyltetrahydrofuran
and 10% by volume of isopropyltoluene. Formulation 5-10 was tested
to demonstrate how the invention enables the formulation of the
ethanol-containing gasoline with a low vapor pressure, wherein the
presence in the motor fuel composition of ethanol does not induce
increase of dry vapor pressure equivalent in comparison to the
source hydrocarbon component (HCC). Moreover, this gasoline secures
decrease of toxic emissions in the exhaust and decrease of the fuel
consumption in comparison with the above mixture RFM 5. The
formulation 5-10 had the following specific properties:
20 density at 15.degree. C., according to ASTM D-4052 764.6
kg/m.sup.3 ; initial boiling point, according to ASTM D
48.9.degree. C.; 86 vaporizable portion - 70.degree. C. 25.3% by
volume; vaporizable portion - 100.degree. C. 50.8% by volume;
vaporizable portion - 150.degree. C. 76.5% by volume; vaporizable
portion - 190.degree. C. 95.6% by volume; final boiling point
204.5.degree. C.; evaporation residue 1.4% by volume; loss by
evaporation 0.5% by volume; oxygen content, according to ASTM
D-4815 4.6% w/w; acidity, according to ASTM D-1613 weight % 0.08;
HAc pH, according to ASTM D-1287 7.5; sulfur content, according to
ASTM D-5453 39 mg/kg; gum content, according to ASTM D-381 1.5
mg/100 ml; water content, according to ASTM D-6304 0.1% w/w;
aromatics, according to SS 155120, 38% by including benzene 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 91.8 ASTM D-2699-86 and ASTM D-2700-86
[1119] The motor fuel Formulation 5-10 was tested as described
previously and gave the following results in comparison (+) or (-)
% with the results for the motor fuel comprising 80% by volume of
reformulated A95 gasoline and 20% by volume of Petroleum
benzine:
21 CO -12.3% HC -6.2%; NO.sub.x unchanged; CO.sub.2 +2.6%; NMHC
-6.4%; Fuel consumption, F.sub.c (1/100 km) +3.7%
[1120] Similar results are obtained when other oxygen-containing
additives of the invention substitute the oxygen-containing
additives of the examples 5-1 to 5-10.
[1121] To prepare all the above fuel formulations 5-1 to 5-10 of
this motor fuel composition, initially the hydrocarbon component
(HCC) which is a mixture of reformulated gasoline and Petroleum
benzine (PB) was mixed with ethanol, to which mixture then was
added the corresponding oxygen-containing additive and
C.sub.8-C.sub.12 hydrocarbons. The motor fuel composition obtained
was then allowed to stand before testing between 1 and 24 hours at
a temperature not lower than -35.degree. C. All the above
formulations were prepared without the use of any mixing
devices.
[1122] The invention demonstrated the possibility to adjust the
vapor pressure of the ethanol-containing motor fuels for the
standard internal combustion spark ignition engines based on
non-standard gasolines having a low vapor pressure.
[1123] FIG. 2 shows the behavior of the dry vapor pressure
equivalent (DVPE) when mixing the hydrocarbon component (HCC),
comprising 80% by volume of reformulated A92 gasoline and 20% by
volume of Petroleum benzine, with the oxygen-containing additive
mixture 5, comprising 40% by volume of ethanol, 20% by volume of
3,3,5-trimethylcyclohexanone, and 20% by volume of naphtha with
boiling temperature 130-170.degree. C. and 20% by volume of
tertbutyltoluene.
[1124] The graph demonstrates that the use of the additive of this
invention enables the attainment of the ethanol-containing
gasolines, the vapor pressure of which does not exceed the vapor
pressure of the source hydrocarbon component (HCC).
[1125] Similar DVPE behavior was demonstrated when mixing the above
oxygen-containing additive with hydrocarbon component (HCC)
comprising 20% by volume of Petroleum benzine (PB) and 80% by
volume of A95 or A98 reformulated gasoline.
[1126] Similar results were obtained when other oxygen-containing
compounds and C.sub.8-C.sub.12 hydrocarbons of this invention were
used in the proportion of the invention to formulate the
oxygen-containing additive, which was then used for preparation of
the ethanol-containing gasolines.
[1127] These gasolines have a vapor 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).
[1128] 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.
* * * * *