U.S. patent application number 09/902678 was filed with the patent office on 2002-03-14 for mixtures suitable as fuel additives.
Invention is credited to Franz, Lothar, Guenther, Wolfgang, Oppenlaender, Knut, Schreyer, Peter, Thomas, Juergen.
Application Number | 20020029512 09/902678 |
Document ID | / |
Family ID | 6483407 |
Filed Date | 2002-03-14 |
United States Patent
Application |
20020029512 |
Kind Code |
A1 |
Thomas, Juergen ; et
al. |
March 14, 2002 |
Mixtures suitable as fuel additives
Abstract
Mixtures of at least one amine, polyamine or alkanolamine and at
least one polyetheramine and their use as additives for gasoline
engine fuels.
Inventors: |
Thomas, Juergen;
(Fussgoenheim, DE) ; Schreyer, Peter; (Weinheim,
DE) ; Oppenlaender, Knut; (Ludwigshafen, DE) ;
Guenther, Wolfgang; (Mettenheim, DE) ; Franz,
Lothar; (Mutterstadt, DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Avenue, N.W.
Washington
DC
20036
US
|
Family ID: |
6483407 |
Appl. No.: |
09/902678 |
Filed: |
July 12, 2001 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09902678 |
Jul 12, 2001 |
|
|
|
08495593 |
Aug 2, 1995 |
|
|
|
6267791 |
|
|
|
|
Current U.S.
Class: |
44/434 ; 44/412;
44/433 |
Current CPC
Class: |
C08K 5/17 20130101; C10L
1/2225 20130101; C10L 1/2383 20130101; C10L 1/22 20130101; C08L
71/02 20130101; C08K 5/17 20130101; C08L 71/02 20130101 |
Class at
Publication: |
44/434 ; 44/433;
44/412 |
International
Class: |
C10L 001/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 20, 1993 |
DE |
P 43 09 074.5 |
Claims
We claim:
1. A mixture suitable as a fuel additive and comprising essentially
A) at least one amine, polyamine or alkanolamine, each of which
carries a hydrocarbon radical having an average molecular weight of
from 500 to 10,000, prepared by hydroformylation of a polyolefin
and amination of the resulting aldehyde and alcohol mixture under
hydrogenating conditions, and B) at least one polyetheramine of the
formula I 4where m is 1 or 2 n is from 1 to 100, R.sup.1 is a
monovalent C.sub.2-C.sub.35-hydrocarbon radical when m is 1 and a
divalent C.sub.2-C.sub.30-hydrocarbon radical when m is 2, and
R.sup.2 and R.sup.3 are each hydrogen, C.sub.1-C.sub.12-alkyl,
C.sub.5-C.sub.7-cycloalkyl, C.sub.6-C.sub.10-aryl, a
polyalkyleneamine radical or alkanolamine radical having from 1 to
5 nitrogen atoms, where the radicals may be identical or different
and, together with the nitrogen atom to which they are bonded, may
form a five-membered or six-membered ring in which further hetero
atoms may be incorporated, and D is C.sub.2-C.sub.5-alkylene.
2. A mixture as claimed in claim 1, wherein the hydrocarbon radical
of the component A has an average molecular weight of from 700 to
1,500.
3. A mixture as claimed in claim 1 or 2, wherein the hydrocarbon
radical of the component A is a polyisobutyl radical.
4. A mixture as claimed in any of claims 1 to 3, wherein, when m is
1, the radical R.sup.1 of component B is phenyl or
C.sub.1-C.sub.20-alkyl-substi- tuted phenyl.
5. A mixture as claimed in any of claims 1 to 4, wherein the
radical D of component B is propylene or butylene.
6. Use of a mixture as claimed in any of claims 1 to 5 as an
additive for fuels for gasoline engines.
7. A fuel for gasoline engines, containing small amounts of A) at
least one amine, polyamine or alkanolamine, each of which carries a
hydrocarbon radical having an average molecular weight of from 500
to 10,000, prepared by hydroformylation of a polyolefin and
amination of the resulting aldehyde and alcohol mixture under
hydrogenating conditions, and B) at least one polyetheramine of the
formula I 5where m is 1 or 2 n is from 1 to 100, R.sup.1 is a
monovalent C.sub.2-C.sub.35-hydrocarbon radical when m is 1 and a
divalent C.sub.2-C.sub.30-hydrocarbon radical when m is 2, and
R.sup.2 and R.sup.3 are each hydrogen, C.sub.1-C.sub.12-alkyl,
C.sub.5-C.sub.7-cycloalkyl, C.sub.6-C.sub.10-aryl, a
polyalkyleneamine radical or alkanolamine radical having from 1 to
5 nitrogen atoms, where the radicals may be identical or different
and, together with the nitrogen atom to which they are bonded, may
form a five-membered or six-membered ring in which further hetero
atoms may be incorporated, and D is C.sub.2-C.sub.5-alkylene.
Description
[0001] The present invention relates to mixtures which are suitable
as fuel additives and comprise essentially
[0002] A) at least one amine, polyamine or alkanolamine, each of
which carries a hydrocarbon radical having an average molecular
weight of from 500 to 10,000 and
[0003] B) at least one polyetheramine of the general formula I
1
[0004] where
[0005] m is 1 or 2
[0006] n is from 1 to 100,
[0007] R.sup.1 is a monovalent C.sub.2-C.sub.35-hydrocarbon radical
when m is 1 and a divalent C.sub.2-C.sub.30-hydrocarbon radical
when m is 2, and
[0008] R.sup.2 and R.sup.3 are each hydrogen,
C.sub.1-C.sub.12-alkyl, C.sub.5-C.sub.7-cycloalkyl,
C.sub.6-C.sub.10-aryl, a polyalkyleneamine radical or alkanolamine
radical having from 1 to 5 nitrogen atoms, where the radicals may
be identical or different and, together with the nitrogen atom to
which they are bonded, may form a five-membered or six-membered
ring in which further hetero atoms may be incorporated, and
[0009] D is C.sub.2-C.sub.5-alkylene.
[0010] The present invention furthermore relates to the use of the
mixtures and fuels for gasoline engines, which contain the
components A and B.
[0011] The carburetor and intake system of gasoline engines as well
as injection systems for metering fuel into gasoline and diesel
engines become increasingly contaminated by impurities which are
caused by dust particles from the air, uncombusted hydrocarbon
residues from the combustion chamber and the vent gases from the
crankshaft casing which are passed into the carburetor.
[0012] The residues adsorb fuel and change the air/fuel ratio
during idling and in the lower part-load range so that the mixture
becomes richer, the combustion more incomplete and in turn the
amounts of uncombusted or partly combusted hydrocarbons in the
exhaust gas become greater and the gasoline consumption
increases.
[0013] It is known that the intake system of gasoline engines can
be kept clean by adding detergents (cf. for example M. Rosenbeck in
Katalysatoren, Tenside, Mineral-oladditive, Editors J. Falbe and U.
Hasserodt, page 223 et seq., Thieme Verlag, Stuttgart 1978, and
Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 16, 719 et
seq., 1990, VCH Verlagsgesellschaft). Emissions and fuel
consumption are thus reduced and the driving characteristics are
improved. The principle of the molecular composition of such
detergents may be described generally as the linking of polar
structures to generally relatively high molecular weight lipophilic
radicals. Typical examples of these are products based on
polyisobutene having amino groups as polar groups, as described in
EP-A 244 616.
[0014] A further important additive component for fuels is a
carrier oil. These carrier oils are as a rule high-boiling
heat-stable liquids. EP-A 356 726 discloses esters of aromatic
polycarboxylic acids with long-chain alcohols as carrier oils. U.S.
Pat. No. 5,112,364 describes polyetheramines having terminal
alkylphenol or alkyl-cyclohexyl groups as fuel additives which have
in particular good valve-cleaning properties.
[0015] WO-A 91/03529 describes the combination of detergents which
carry certain amino groups with poly-ether alcohols as carrier
oils. This combination in particular contributes to a lesser extent
than its individual components to the octane requirement increase
(ORI), which is due to deposits of the fuel or the additives on
engine parts. A new engine reaches its final octane requirement
only after a considerable running time, after which said
requirement may be considerably higher than at the beginning. In
general, additives should at least not reinforce this effect.
[0016] A considerable disadvantage of the stated combination of
additives is the unsatisfactory miscibility of the detergent with
the carrier oil. Cloudy mixtures which cannot be added to the fuels
frequently result. Phase separation frequently occurs in these
mixtures after prolonged stoppage. The distribution of the
detergent in the mixture is thus inhomogeneous. In practice,
however, the additive packages required are those which contain all
components in dissolved form and which can be added to the fuel in
one process step.
[0017] It is an object of the present invention to provide a
combination of a detergent and a carrier oil component which, in
addition to the properties of having a valve-cleaning effect in
fuels and not adversely affecting the ORI compared with fuels
without additives, remain thoroughly miscible with one another.
[0018] We have found that this object is achieved by the mixtures
defined above, which contain a detergent A and a polyetheramine B
of the formula I. We have also found the use of these mixtures, and
fuels which contain the components A and B.
[0019] Component A
[0020] The component A is effective in fuels primarily as a
detergent. Suitable components A are amines, polyamines or
alkanolamines which possess a hydrocarbon radical having an average
molecular weight of from 500 to 10,000, preferably from 600 to
2,500, particularly preferably from 700 to 1,500.
[0021] The hydrocarbon radical is, as a rule, branched. In general,
it is a radical which is obtainable by polymerization of olefins.
These olefins are preferably C.sub.2-C.sub.6-olefins, such as
ethylene, propylene, 1-butene, 1-pentene and particularly
preferably isobutene. Both homopolymers and copolymers, for example
polymers of from 70 to 95 mol % of isobutene and from 5 to 30 mol %
of 1-butene, are suitable. As a result of their preparation
process, these polyolefins generally consist of a mixture of
compounds having different molecular weights.
[0022] After chlorination, these polyolefins can be reacted with
amines in a conventional manner. However, hydroformylation of the
polyolefin and amination of the resulting aldehyde and alcohol
mixture under hydrogenation conditions (cf. EP-A 244 616) are
preferred since this method leads to chlorine-free products. The
amino group of the detergent A is derived from conventional amines,
such as ammonia, primary amines, such as methylamine, ethylamine,
butylamine, hexylamine or octylamine, secondary amines, such as
dimethyhlamine, diethylamine, dibutylamine or dioctylamine, and
heterocycles, such as piperazine, pyrrolidine or morpholine, which
may carry further inert substituents. Polyamines, such as
ethylenediamine, propylenediamine, diethylenetriamine,
triethylenetetramine, hexamethylenediamine, tetraethylenepentamine
and dimethylaminopropylamine, as well as various alkylene-carrying
polyamines, such as ethylenepropylenetriamine, may also be
mentioned as starting materials for the preparation of the
detergents A. Examples here are alkanolmonoamines, such as
ethanolamine, and alkanolpolyamines, such as
aminoethylethanolamine. Among these, the polyamines are preferred,
in particular ethylenediamine, diethylenetriamine and
triethylenetetramine. However, ammonia is very particularly
preferred.
[0023] Component B
[0024] The novel mixture contains, as the carrier oil, a
polyetheramine of the general formula I 2
[0025] Specifically, the variables have the following meanings:
[0026] m is 1 or 2, preferably 1.
[0027] n indicates the number of repeating oxyalkylene units and is
from 1 to 100, preferably from 5 to 50, in particular from 7 to
30.
[0028] The radicals R.sup.1 are different hydrocarbon radicals.
Where m is 1, R.sup.1 is a monovalent C.sub.2-C.sub.35-hydrocarbon
radical. Straight-chain aliphatic radicals, such as n-hexyl,
n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and n-tridecyl, are
suitable, as well as branched aliphatic radicals, such as
2-ethylhexyl, isobutyl and tert-butyl. Aryl radicals, such as
phenyl, and alkyl-substituted phenyl radicals, including in
particular C.sub.6-C.sub.16-substituted phenyl radicals, such as
octylphenyl, nonylphenyl and dodecylphenyl, may also be mentioned.
The alkyl radicals are preferably in the 2- and 4-position of the
phenyl ring. Commercial mixtures of the positional isomers may also
be used. Compounds which are polysubstituted by alkyl are also
suitable.
[0029] Where m is 2, R.sup.1 is a divalent
C.sub.2-C.sub.30-hydrocarbon radical, such as alkylene, eg.
ethylene, propylene, butylene or hexylene. However, radicals which
are derived from polyphenols, such as bisphenol A
(2,2-bis-(4-hydroxyphenyl)-propane,
1,1-bis-(4-hydroxyphenyl)-ethane,
1,1-bis-(4-hydroxyphenyl)-isobutane,
2,2-bis-(4-hydroxy-3-tert-butylpheny- l)-propane and
1,5-dihydroxy-naphthalene by formal elimination of the hydroxyl
groups are preferred.
[0030] R.sup.2 and R.sup.3 may be identical or different. They are
each hydrogen, C.sub.1-C.sub.12-alkyl, such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, hexyl or octyl,
C.sub.5-C.sub.7-cycloalkyl, such as cyclopentyl or cyclohexyl,
C.sub.6-C.sub.10-aryl, such as phenyl, polyalkyleneamine radicals
which have from 1 to 5 nitrogen atoms and are derived from
polyalkyleneamines such as diethyleneamine, triethylenediamine,
tetraethylenetriamine, tetraethylenepentamine and
dimethylaminopropylamine. Suitable alkanolamines are
alkanolmonoamines, such as ethanolamine, and alkanolpolyamines,
such as aminoethylethanolamine. Furthermore, the radicals together
with the nitrogen atom to which they are bonded may form a
five-membered or six-membered ring, such as piperidine or
piperazine. The heterocyclic structure may carry inert
substituents, as in 2-amino-ethylpiperazine. The ring may contain
further hetero atoms, such as oxygen, as in morpholine.
[0031] D is C.sub.2-C.sub.5-alkylene, such as ethylene,
1,2-propylene or butylene. C.sub.3- and C.sub.4-alkylene groups are
preferred. Where n is greater than 1, the radicals D may be
identical or different. The units --(OD).sub.n-- may be present as
homopolymers or as block copolymers. However, polymers in which the
various radicals are randomly distributed are most easily
obtainable.
[0032] The polyetheramines I are known per se or can be prepared by
known methods (U.S. Pat. No. 5,112,364).
[0033] For this purpose, an alcohol R.sup.1--OH is generally
reacted with n equivalents of an alkylene oxide in the presence of
a strong base, such as potassium tert-butylate at elevated
temperatures with formulation of a polyether of the formula II
3
[0034] The variables have the same meanings as stated above. These
polyethers are then subjected to amination by a conventional method
in a further reaction stage, generally without further
pretreatment. Amination is understood here as meaning the reaction
of the polyether with ammonia or with a primary amine or polyamine,
the terminal hydroxyl group being replaced by an amino group with
elimination of water (Houben-Weyl, Methoden der Organischen Chemie,
Volume 11/1, Chapter IIb, pages 108-134, 4th Edition,
Thieme-Verlag, (1957)).
[0035] The novel mixtures consist essentially of the detergent A
and the polyetheramine I as component B. The mixtures contain, as a
rule, from 15 to 95, preferably from 30 to 80, % by weight of
component A and from 5 to 85, preferably from 20 to 70, % by weight
of component B.
[0036] In addition, the novel mixtures may contain further
components C, the amounts of C being from 0 to 40, preferably from
0 to 10, % by weight, based on the total weight of components A and
B. These components C have only a slight influence on the
properties of the novel mixtures when the latter are used in
fuels.
[0037] The component C comprises conventional additives for
mixtures which are added to fuels. They are understood as being
corrosion inhibitors, demulsifiers, detergents or dispersants, such
as amides and imides of polyisobutylsuccinic anhydride, and also
carrier oils, such as esters of carboxylic acids or polycarboxylic
acids and alkanols or polyols (cf. DE-A 38 38 918).
[0038] The present invention furthermore relates to fuels for
gasoline engines, which contain small amounts of the components A
and B.
[0039] Suitable fuels are leaded and unleaded regular and
premium-grade gasoline. The gasolines may contain components other
than hydrocarbons, for example alcohols, such as methanol, ethanol
or tert-butanol, and ethers, such as methyl tert-butyl ether.
[0040] The novel fuels contain each of the components A and B in
general in amounts of from 10 to 5,000 ppm, preferably from 50 to
1,000 ppm, based on the total weight. In addition to the components
C described above, the novel fuels may also contain antioxidants,
eg. N,N'-di-sec-butyl-para-phenylenediamine, as stabilizers, eg.
N,N'-disalicylidene-1,2-diaminopropane.
[0041] The components A and B can be mixed to give clear,
homogeneous solutions. Fuels to which the latter have been added
result in substantially less valve deposits than the pure fuels.
Furthermore, the additives do not contribute to an octane
requirement increase (ORI).
EXAMPLES
Preparation Examples
Example 1
[0042] Preparation of a Polyether II, where m is 1, n is 24,
R.sup.1 is Nonylphenyl and D is 1,2-propylene
[0043] 740 g (3.36 mol) of nonylphenol and 55 g of potassium
tert-butylate are reacted with 4.68 kg (80.6 mol) of propylene
oxide at 130.degree. C. and 4 bar while stirring. After 3.5 hours,
the mixture was worked up to obtain the product. 5.40 kg of the
polyether remained.
Example 2
[0044] Preparation of a Polyetheramine I, Where the Variables Have
the Meanings Stated in Example 1 and Furthermore R.sup.2 and
R.sup.3 are Each Hydrogen
[0045] 362 g (0.3 mol) of the polyether according to Example 1 were
heated with 500 ml of ammonia and 50 g of Raney nickel at
225.degree. C. and at a hydrogen pressure of 280 bar for 4 hours.
330 g of product were obtained and the degree of amination was 96%
(total amine number 44.6 mg KOH/g).
[0046] A polyisobutyamine PIBA having an average molecular weight
of 1,000 (prepared as described in EP-A 244 616) was used as
component A in the experiments below.
Use Examples
[0047] Mixing Experiments
[0048] The polyether or aminated polyether prepared in Examples 1
and 2, respectively, was mixed with PIBA in the weight ratios 1:1,
2:1 and 1:2, and the homogeneity of the solution was visually
assessed.
1 Mixing ratio 2:1 1:1 1:2 PIBA + polyether very cloudy 2 phases 2
phases solution PIBA + aminated clear, homo- clear, homo- clear,
homo- polyether geneous geneous geneous solution solution
solution
[0049] Engine Test
[0050] Determination of Valve Deposits in an Opel Kadett according
to CEC-F-02-T-79
[0051] In the engine tests, combinations of PIBA with the polyether
according to Example 1 or with the aminated polyether according to
Example 2 were tested for their efficiency in keeping the intake
valves clean.
[0052] Fuel: unleaded premium-grade European gasoline
2 Amount of additive Average valve Product (mg/kg) deposits in mg
Basic value (without additive) -- 386 PIBA + 200 81 polyether
according to Example 1 200 PIBA + 200 0 aminated polyether
according 200 to Example 2
[0053] The substantially higher efficiency of the novel combination
of PIBA with the aminated polyether compared with the combination
of PIBA with the polyether according to Example 1 is evident.
[0054] Determination of the Octane Requirement Increase ORI General
Method of Measurement:
[0055] The octane requirement increase is measured in a 400 hour
long-term test in a Mercedes-Benz M 102 E engine. In the engine
used, the cylinder head is equipped with 4 pressure sensors. These
sensors are installed so that the pressure membranes are mounted
virtually without a straight channel in the wall of the combustion
chamber. It is thus possible to record the pressure in the
combustion chamber without whistle vibrations which falsify the
result.
[0056] With the indexing apparatus connected for evaluation and
consisting of 4 quartz sensors and a commercial indexing apparatus
(AVL-Indiskop), the pressure variations in the range of interest
for each combustion, extending from a crank angle of 300 before the
upper dead center to a crank angle of 300 after the upper dead
center, can be monitored. A built-in computer permits the
evaluation of the course of the combustion. The pressure signals of
the individual cylinders can be averaged and can be evaluated in
various computational operations. It has proven advantageous to
apply the heat law in order to measure knocking in the limiting
region.
[0057] This function serves for rapid calculation of the heat curve
(=heat liberation per .degree. crank angle), of the integerated
heat curve (cumulative heat liberation) and of the curve for the
mean gas temperature. This is a simplified algorithm which
calculates, from the pressure variation in the combustion chamber,
the energy effectively supplied to the gas. The heat actually
liberated during the combustion is higher by an amount
corresponding to the energy loss through the wall (about 20%).
[0058] The heat liberation in the interval considered is calculated
from the difference between the actual pressure at the end of the
interval and the pressure value resulting in the case of pure
adiabetic compression/expansion in the interval.
Q.sub.1-2=m.multidot.c.sub.v(T.sub.2-T.sub.2') 1 Q 1 - 2 = m c v (
T 2 - T 2 ' ) T 2 = P 2 V 2 m R T 2 ' = P 2 ' V 2 ' m R 2 P 2 ' = P
1 ' ( V 1 V 2 ) n P = Actual pressure P ' = Pressure with adiabetic
compression / expansion m = Mass of the fuel / air mixture c v =
Specific heat v = constant R = Gas constant n = Polytropic exponent
Q 1 - 2 = C v R V 2 ( P 2 - P 1 ( V 1 V 2 ) n )
[0059] Approximate values for c.sub.v and n.
[0060] c.sub.v=0.7+T 0.001.multidot.(0.155+A), A=0.1 for gasoline
engines 3 n = 1 + 0.2888 c v
[0061] The values thus calculated for the energy conversion
[0062] in 4 KJ kg .degree. crank angle or KJ m 3 .degree. crank
angle
[0063] clearly indicate disturbances in the energy conversion due
to combustion with knocking.
[0064] It is thus possible to recognize the head threshold with
minimum knocking. By means of existing fuels having known octane
numbers, the octane requirement of the engine under certain load
conditions can thus be determined readily and reproducibly.
[0065] Fuel: unleaded premium-grade European gasoline
3 Amount of Octane require- additive ment increase Product (mg/kg)
(.DELTA. ON) Basic value (without additive) -- 3.1 PIBA + 200 8.1
polyether according to Example 1 200 PIBA + 200 2.9 aminated
polyether according 200 to Example 2
[0066] While the combination of PIBA with polyether leads to an
increase of 4.3 octane numbers and hence an increase by more than 1
octane number compared with the value for the fuel without an
additive, an octane requirement increase of only 2.9 was measured
for the combination of PIBA with the aminated polyether.
* * * * *