[0001] This invention relates generally to improving the stability of middle distillate
fuels and more particularly to stabilized middle distillate fuel compositions which
contain a combination of N,N-dimethylcyclohexyl amine and a Mannich Base.
[0002] Middle distillate fuels such as diesel oil, fuel oil, jet fuel and kerosene when
stored for long periods of time are subject to the formation of color and solid deposits.
The deposits accumulate on filters causing the filters to become plugged. Various
additives and combinations of additives have been employed to reduce color and deposit
formation. For example: U.S. Patent 2,984,550 discloses the use of Mannich bases derived
from phenols, formaldehyde and polyamines for stabilization; U.S. Patent 3,490,882
discloses stabilized petroleum distillate fuel oils containing N,N-dimethylcyclohexylamine
antioxidant and a N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine metal deactivator
such as N,N′-disalicylidene-1,2-propylenediamine; U.S. Patent 4,166,726 discloses
a fuel additive which is a mixture of a polyalkylene amine and a Mannich Base; and
U.S. Patents 4,501,595 and 4,533,361 disclose diesel oil which contains a condensate
of tetraethylene pentamine, paraformaldehyde, a hindered phenol such as 2,6-di-t-butylphenol
and polyisobutenyl succinic anhydride.
[0003] The effectiveness of any particular type of additive combination can vary with different
fuel stocks and combinations which are more effective at the same total additive concentration
reduce treatment cost. We have now discovered novel, synergistic additive combinations
which include certain Mannich Bases and provide middle distillate fuels having generally
improved storage stability compared to fuels containing the same total concentrations
of either N,N-dimethylcyclohexylamine antioxidant alone or N,N-dimethylcyclohexylamine
in combination with an N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine metal
deactivator.
[0004] In accordance with this invention, there is provided a fuel additive concentrate
comprising a mixture of N,N-dimethylcyclohexylamine and a Mannich Base which is the
reaction product of an aldehyde, an amine and an alkyl phenol selected from (a) hindered
phenol having the formula:
where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl,
provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and
R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
where R₄ is C₉ to C₃₀ alkyl.
The concentrate can also contain a N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine
metal deactivator such as N,N′-disalicylidene-1,2-propylenediamine. Also provided
is a stabilized fuel containing from 1 to 1400 mgs/liter of N,N-dimethylcyclohexylamine,
from 0.5 to 1100 mgs/liter of Mannich Base and from 0 to 400 mgs/liter of an N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine.
[0005] The N,N-dimethylcyclohexylamine component of the compositions of the invention is
a commercially available fuel antioxidant.
[0006] The N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine component, in which, typically,
the arylidene radical contains 6-7 carbon atoms and the alkylene radical contains
2-3 carbon atoms, is a metal deactivator whose presence in combination with the other
components provides fuel compositions of the invention having the most improved stability.
The preferred metal deactivator is N,N′-disalicylidene-1,2-propylenediamine which
is commercially available.
[0007] The Mannich Base component of the invention is produced by the Mannich condensation
reaction of a hindered or p-alkyl phenol, an aldehyde, such as formaldehyde, ethanal,
propanal, and butanal (preferably formaldehyde in its monomeric form or paraformaldehyde)
and primary and secondary amines.
[0008] The hindered phenols which are useful in preparing the Mannich Base component of
the invention are phenols which are characterized by the presence of at least one
and preferably two ortho-t-butyl, t-amyl, and/or isopropyl groups. Specific examples
of such hindered phenols include: 2,4-di-t-butylphenol, 2,4-diisopropylphenol, 2,6-diisopropylphenol,
2-t-butylphenol, and 2-t-amylphenol with 2,6-di-t-butylphenol being most preferred.
[0009] The p-alkyl phenols which are useful in preparing the Mannich Base component of the
invention are those which contain from 9 to 30 carbons which can be arranged in either
a straight or a branched chain. Preferred phenols are C₉ to C₁₂ p-alkylphenols such
as, for example, p-nonylphenol and p-dodecylphenol.
[0010] The amines which are useful in preparing the Mannich Base component of the invention
are primary and secondary amines which can be selected from one or more of:
A. alkyl monoamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl, and R₆ is selected from C₁ to C₁₄
alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
B. alkyl diamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl, R₈ is C₁ to C₆ alkylene and A and
B are independently selected from H, C₁ to C₅ alkyl, monohydroxysubstituted C₁ to
C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
D. cyclic amines of the formula;
where n and m are independently integers from 1 to 3, X is selected from CH₂, O,
S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10. The alkyl groups can have a branched chain.
[0011] Specific examples of such amines include 1,3-diaminopropane, 1,2 diaminopropane,
dimethylamine, diethylamine, dipropylamine, dibutylamine, N,N-dimethyl-1,3-diaminopropane,
1,1-dimethyldodecylamine, mixed C₁₂-C₁₄ t-alkyl amines, 2-methyl-1,5-pentadiamine,
ethylenediamine; cyclic amines such as piperazine, aminoethylpiperazine, morpholine
and thiomorpholine; and ethylene polyamines such as diethylene triamine and triethylene
tetraamine.
[0012] The Mannich Base can be formed by reacting from 1 to 5 moles of aldehyde, from about
1 to 2 moles of amine and from 1 to 4 moles of phenol at a temperature of from 0°C
to 150°C for 0.5 to 10 hours. An inert solvent such as isopropanol can be used which
is distilled from the product along with water formed in the reaction.
[0013] The Mannich Base product is usually a mixture of materials which may contain unreacted
ingredients, especially the phenol. The Mannich Bases can be isolated from the product
mixture but the product mixture itself can conveniently be used in forming the compositions
of the invention. Examples of Mannich reactions and products are illustrated below:
where R₁, R₂, R₄, R₅ and R₆ are as defined above.
[0014] The additive mixtures of the invention are usually prepared and marketed in the form
of concentrates for addition to the fuel by the customer although the individual
components could be added directly into the fuel. Suitable proportions of additives
in the concentrates of the invention, based on the total weight of concentrate, include
from 25 to 95 wt% N,N-dimethylcyclohexylamine, from 0 to 25 wt% N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine
and, from 5 to 75 wt% Mannich Base.
[0015] The concentrates are added to the fuel in effective amounts to provide improved stability.
Suitable amounts of additive concentrate in the fuel are from 1 to 500 pounds per
thousand barrels (Ptbs) (3 to 1500 mgs/liter, preferred 2.5 to 100 Ptbs or 8 to 300
mgs/liter). This will provide a stabilized fuel containing from 1 to 1400 mgs/liter
(preferred 2 to 250 mgs/liter) N,N-dimethylcyclohexylamine, from 0 to 400 mgs/liter
(preferred 0 to 100 mgs/liter) N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine
metal deactivator and from 1 to 1100 mgs/liter (preferred 1 to 250 mgs/liter) of Mannich
Base. When used, the metal deactivator is present in amounts of 1.0% to 25 wt% of
concentrate or .3 to 400 mgs/liter of fuel. The concentrates can also contain an inert
diluent or solvent which can be, for example, an aliphatic hydrocarbon such as kerosene
or an aromatic hydrocarbon such as xylene.
[0016] The middle distillate fuels whose stability is improved by the invention typically
include those boiling within a temperature range of 150°-400°C which may commonly
be labeled as kerosene, fuel oil, diesel oil, No. 1-D, or No. 2-D.
[0017] The compositions of the invention are further illustrated by, but are not intended
to be limited to, the following examples wherein parts are parts by weight unless
otherwise indicated.
Example 1
[0018] A Mannich Base reaction product of formaldehyde, 1,3-diaminopropane and 2,6-di-t-butylphenol
is prepared by the following process.
[0019] Dissolve 103 grams (0.5 mole) of 2,6-di-t-butylphenol in 100 grams of isopropyl
alcohol (IPA) in a 500 ml round bottom flask. Add 18.5 grams (0.25 mole) of 1,3-diaminopropane
dropwise over 15 minutes while the contents of the flask are stirred. There is an
exotherm observed as the amine is added. Cool the contents of the flask to below 30°C
and add a 10% excess, (44.6 grams 0.55 mole) of 37% aqueous formaldehyde solution
dropwise over 30 minutes while maintaining the temperature below 30°C. Heat the contents
of the flask to reflux and continue to reflux for one hour. Switch from reflux to
distillation and distill off IPA/water mixture to 105°C. Apply 28 in. Hg vacuum to
remove residual materials. The total product yield is 122.2 or 96% of theory which
contains compounds of the Structure III and IV.
[0020] Additive blends of the reaction product were prepared and tested in different fuels
using both the D 4625 43°C (110°F) Storage Stability Test, in which the color change
(using ASTM D1500) and the total insolubles in the fuel (reported in mg/100 ml) are
determined on 400 ml samples stored for 13 weeks in the dark and the F-21-61 149°C
(300°F) Accelerated Stability Test in which the color change and insoluble gums are
determined on 50 ml samples heated to 149°C for a selected time, which was 90 minutes,
allowed to cool in the dark, tested for color (ASTM D1500), and then filtered (using
a 4.25 cm Whatman #1 filter paper) and the filtrate discarded. The filter is washed
clean of fuel with isooctane and measured for deposits by comparison with a set of
reference papers. The blend compositions and test results in comparison to untreated
fuel and blends without the Mannich Base product are reported in Table I below.
TABLE I
Composition in Pounds Per Thousand Barrels |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
DMCA¹ |
0.0 |
5.0 |
4.0 |
4.75 |
3.80 |
0.0 |
4.75 |
3.8 |
0.0 |
9.5 |
7.6 |
0.0 |
2.38 |
1.90 |
4.75 |
3.80 |
MDA² |
0.0 |
0.0 |
0.0 |
0.25 |
0.25 |
0.0 |
0.25 |
0.24 |
0.0 |
0.5 |
0.5 |
0.0 |
0.12 |
0.12 |
0.25 |
0.24 |
Mannich Base |
0.0 |
0.0 |
1.0 |
0.00 |
0.95 |
0.0 |
0.0 |
0.96 |
0.0 |
0.0 |
1.9 |
0.0 |
0.00 |
0.48 |
0.00 |
0.96 |
Total Additives |
0.0 |
5.0 |
5.0 |
5.0 |
5.0 |
0.0 |
5.0 |
5.0 |
0.0 |
10.0 |
10.0 |
0.0 |
2.5 |
2.5 |
5.0 |
5.0 |
Test Results |
149°C (F-21-61) |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
Color |
L7 |
L3.5 |
2.5 |
L3 |
2 |
8 |
3 |
3 |
8 |
L2.5 |
2 |
L2.5 |
2 |
2 |
2.5 |
L2.5 |
Deposit |
13 |
5 |
4 |
4 |
2 |
17 |
10 |
5 |
17 |
5 |
3 |
6 |
4 |
4 |
4 |
4 |
43°C (D 4625) |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
Color |
L5 |
4 |
4 |
4 |
L4 |
L3.5 |
L3.5 |
L3.5 |
L3.5 |
L3.5 |
L3.5 |
2.5 |
L2.5 |
L2.5 |
L2.5 |
L2.5 |
Deposit |
6.8 |
3.2 |
2.4 |
2.5 |
1.8 |
7.9 |
4 |
4.7 |
6.7 |
3 |
2.1 |
2.2 |
2 |
1.6 |
1.3 |
1 |
L = less than |
¹N,N-dimethylcyclohexylamine |
²N,N′-disalicylidene-1,2-propylenediamine |
Fuel #1 is Midwest Refinery |
Fuel #2 is Mid-Continent #2 Diesel (Corning Crude) |
Fuel #3 is Mid-Continent #2 Diesel (Ill. Basin Crude) |
Fuel #4 is Midwest #2 Diesel (KS/Tx Crude) |
[0021] A significant difference in stability at 149°C is indicated by a color difference
of about 1/2 number and/or a deposit difference of 2 numbers and a significant difference
in stability at 43°C is indicated by a color difference of about 1/2 number and a
deposit difference of 20%. The results in Table I show that the blends of the invention
which contain Mannich Base in addition to DMCA or DMCA and MDA gave significantly
better overall stability when compared to comparable blends which did not contain
the Mannich Base, for example, blend 3 vs blend 2 and blend 5 vs blend 4 of Fuel #1.
Example 2
[0022] A Mannich Base reaction product of formaldehyde, dimethylamine, and 2,6-di-t-butylphenol
is prepared by the following process.
[0023] Dissolve 103 grams (0.5 mole) of 2,6-di-t-butylphenol in 100 grams of IPA in a 500
ml round bottom flask and add 72 grams (0.64 mole) of a 40% aqueous dimethylamine
solution. Cool the mixture to about 30°C and add dropwise with stirring 44.6 grams
(0.55 mole) of 37% formaldehyde while keeping the mixture at a temperature below 40°C.
Heat the mixture to reflux and reflux for 4 hours. Remove IPA/water by distillation
and apply vacuum to remove residual materials. The product yield is 113 grams or 86%
of theory which contains N,N-dimethyl-3,5-di-t-butyl4-hydroxybenzylamine.
[0024] Additive blends of the above reaction product were prepared and tested in different
fuels using the test procedures described in Example 1. The blend compositions and
test results in comparison to untreated fuel and blends which did not contain the
Mannich Base product are reported in Table II below.
TABLE II
Composition in Pounds Per Thousand Barrels |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
DMCA |
0.0 |
5.0 |
4.0 |
4.75 |
3.80 |
0.0 |
9.5 |
7.6 |
0.0 |
28.5 |
22.8 |
0.0 |
2.38 |
1.90 |
4.75 |
3.80 |
MDA |
0.0 |
0.0 |
0.0 |
0.25 |
0.25 |
0.0 |
0.5 |
0.5 |
0.0 |
1.5 |
1.5 |
0.0 |
0.12 |
0.12 |
0.25 |
0.24 |
Mannich Base |
0.0 |
0.0 |
1.0 |
0.00 |
0.95 |
0.0 |
0.0 |
1.9 |
0.0 |
0.0 |
5.7 |
0.0 |
0.00 |
0.48 |
0.00 |
0.96 |
Total Additives |
0.0 |
5.0 |
5.0 |
5.0 |
5.0 |
0.0 |
10.0 |
10.0 |
0.0 |
30.0 |
30.0 |
0.0 |
2.5 |
2.5 |
5.0 |
5.0 |
Test Results |
149°C (F-21-61) |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
Color |
L7 |
L3.5 |
3 |
L3 |
L3 |
8 |
3 |
3 |
4.5 |
L4 |
3.5 |
L2.5 |
2 |
L2.5 |
2.5 |
L2.5 |
Deposit |
13 |
5 |
6 |
4 |
4 |
17 |
10 |
6 |
5 |
3 |
3 |
6 |
4 |
5 |
4 |
3 |
43°C (D 4625) |
|
Fuel #1 |
Fuel #2 |
Fuel #3 |
Fuel #4 |
Components |
1 |
2 |
3 |
4 |
5 |
1 |
2 |
3 |
1 |
2 |
3 |
1 |
2 |
3 |
4 |
5 |
Color |
L5 |
4 |
4 |
4 |
4 |
L3.5 |
L3.5 |
L3.5 |
-- |
-- |
-- |
2.5 |
L2.5 |
L3 |
L2.5 |
L2.5 |
Deposit |
6.8 |
3.2 |
2.8 |
2.5 |
2 |
6.7 |
4 |
3.9 |
-- |
-- |
-- |
2.2 |
2 |
1.9 |
1.3 |
0.9 |
The fuels were the same as in Example 1 except that Fuel #3 is a fuel containing unhydrotreated
residual cracked stock. |
[0025] The results indicated that the blends containing Mannich Base gave fuels having significantly
improved stability except in the case of Fuel #4 where the results were mixed.
Example 3
[0026] A Mannich Base reaction product of formaldehyde, C₁₂-C₁₄ t-alkyl amine mixture (Primene
81R) and 2,6-di-t-butyl phenol is prepared by the process described in Example 2
using 95.5 grams (0.5 mole) of Primene 81R in place of the dimethylamine. The product
yield is 200 grams or 82% of theory which contains N-[3,5-di-t-butyl-4-hydroxybenzyl]-mixed
C₁₂-C₁₄ t-alkyl amines.
[0027] Additive blends of the above reaction product were prepared and tested in #2 diesel
fuel using the test procedures described in Example 1. The blend compositions and
test results are reported in Table III below.
TABLE III
Composition Pounds Per Thousand Barrels |
Components |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
DMCA |
0.0 |
9.5 |
0.0 |
4.75 |
19.0 |
0.0 |
9.5 |
MDA |
0.0 |
0.5 |
0.5 |
0.50 |
1.0 |
1.0 |
1.0 |
Mannich Base |
0.0 |
0.0 |
9.5 |
4.75 |
0.0 |
19.0 |
9.5 |
Total Additives |
0.0 |
10.0 |
10.0 |
10.0 |
20.0 |
20.0 |
20.0 |
Test Results |
149°C (F-21-61) |
Components |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
Color |
L5.5 |
L4.5 |
L5 |
L4.5 |
L4.5 |
L5 |
L4.5 |
Deposit |
8 |
6 |
4 |
3 |
4 |
3 |
2 |
43°C (D 4625) |
Components |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
Color |
L6.5 |
L6 |
6 |
L6 |
5.5 |
L6 |
L5.5 |
Deposit |
8.3 |
3.2 |
5 |
2.8 |
3.3 |
5 |
3 |
[0028] The results indicate that blends 4 and 7 according to the invention which contain
the Mannich Base in addition to DMCA and MDA have better stability at the same total
additive levels compared to blends 2 and 5 containing only DMCA and MDA.
Example 4
[0029] A Mannich Base reaction product of formaldehyde, 1,2-diaminopropane, and 2,6-di-t-butyl
phenol is prepared by the following process.
[0030] Dissolve 103 gm (0.5 mole) of 2,6-di-t-butyl phenol in 100 grams of IPA in a 500
ml roundbottom flask and add 18.5 grams (0.25) moles of 1,2-diaminopropane. Cool this
mixture to about 30°C and add dropwise with stirring 44.6 grams (0.55 mole) of 37%
formaldehyde while keeping the temperature of the mixture below 40°C. Heat the mixture
to reflux and reflux for 1 hour. Remove IPA/water by distillation and apply vacuum
to remove residual materials.
[0031] Additive blends of the above reaction product were prepared and tested in Fuel #1
fuel using the test procedures described in Example 1. The blend compositions and
results are reported in Table IV below.
TABLE IV
Composition Pounds Per Thousand Barrels |
Components |
1 |
2 |
3 |
4 |
5 |
DMCA |
0.0 |
5.0 |
4.75 |
4.0 |
3.8 |
MDA |
0.0 |
0.0 |
0.25 |
0.0 |
0.25 |
Mannich Base |
0.0 |
0.0 |
0.00 |
1.0 |
0.95 |
Total Additives |
0.0 |
5.0 |
5.0 |
5.0 |
5.0 |
Test Results |
149°C (F-21-61) |
Components |
1 |
2 |
3 |
4 |
5 |
Color |
L7 |
L3.5 |
L3 |
L3 |
L2.5 |
Deposit |
13 |
5 |
4 |
3 |
3 |
43°C (D 4625) |
Components |
1 |
2 |
3 |
4 |
5 |
Color |
L5 |
4 |
4 |
4 |
L4 |
Deposit |
6.8 |
3.2 |
2.5 |
2.6 |
1.7 |
[0032] The results indicate that blend 4 of the invention containing the Mannich Base has
improved stability compound to blend 2 which containing DMCA alone. Blend 5 containing
the Mannich Base has improved stability over blend 3 which contained DMCA and MDA
alone.
Example 5
[0033] A Mannich Base reaction product of formaldehyde, N,N-dimethyl-1,3-diaminopropane,
and p-dodecylphenol was prepared by the following procedure.
[0034] Combine 262.4 grams (1.0 mole) of the alkyl (C₁₂) phenol with 102.2 grams (1.0 mole)
of N,N-dimethyl-1,3-diamino-propane and add 89.2 grams (1.1 mole) of 37% formaldehyde
with stirring while keeping the temperature below 40°C. Heat the mixture to 100°C
for two hours and then remove water by distillation (100°C - 28 in vacuum). The product
yield is 176 grams or 93% of theory which contains N,N-dimethyl-N′-[2 hydroxy-5-dodecylbenzyl]-1,3-diaminopropane.
[0035] Additive blends of the above reaction product were prepared and tested in midcontinent
#2 diesel fuel using the test procedures described in Example 1. The blend compositions
and results are reported on Table V below.
TABLE V
Composition Pounds Per Thousand Barrels |
Components |
1 |
2 |
3 |
4 |
5 |
DMCA |
0.0 |
4.75 |
2.05 |
9.5 |
4.5 |
MDA |
0.0 |
0.25 |
0.25 |
0.5 |
0.5 |
Mannich Base |
0.0 |
0.00 |
2.70 |
0.0 |
5.4 |
Total Additives |
0.0 |
5.0 |
5.0 |
10.0 |
10.0 |
Test Results |
149°C (F-21-61) |
Components |
1 |
2 |
3 |
4 |
5 |
Color |
8 |
3 |
L3 |
L2.5 |
L2.5 |
Deposit |
13 |
10 |
5 |
5 |
5 |
43°C (D 4625) |
Components |
1 |
2 |
3 |
4 |
5 |
Color |
L3.5 |
L3.5 |
3 |
L3.5 |
L3.5 |
Deposit |
6 |
4 |
3.5 |
3 |
2.4 |
[0036] The results indicate that blends 3 and 5 of the invention have over-all improved
stability compared to blends at the same total additive level which did not include
the Mannich Base.
1. A fuel additive concentrate comprising a mixture of N,N-dimethylcyclohexylamine
and a Mannich Base which is the reaction product of an aldehyde, a primary or secondary
amine and an alkyl phenol selected from (a) hindered phenol having the formula:
where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl,
provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and
R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
where R₄ is C₉ to C₃₀ alkyl; said concentrate containing, based on the total weight
of concentrate, from 25 to 95 wt% N,N-dimethylcyclohexylamine from 5 to 75 wt% Mannich
Base.
2. The concentrate of claim 1 wherein the concentrate also contains from 1 to 25
wt% N,N′-di(ortho-hydroxyarylidene)-1,2-alkylenediamine metal deactivator.
3. The concentrate of claim 1 or 2 wherein the aldehyde is formaldehyde, and the amine
is selected from one or more of:
A. alkyl monoamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl, and R₆ is selected from C₁ to C₁₄
alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
B. alkyl diamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl, R₈ is C₁ to C₆ alkylene and A and
B are independently selected from H, C₁ to C₅ alkyl, mono-hydroxysubstituted C₁ to
C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
D. cyclic amines of the formula;
where n and m are independently intergers from 1 to 3, X is selected from CH₂, 0,
S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10.
4. The concentrate of any of the preceding claims wherein the phenol is a hindered
phenol, and the Mannich Base comprises N-[3,5-di-t-butyl-4-hydroxybenzyl]-mixed C₁₂
to C₁₄ t-alkyl amines, N,N-dimethyl-3,5-di-t-butyl-4-hydroxybenzylamine, a compound
of the formula:
where R₁ and R₂ are independently selected from hydrogen, t-butyl, t-amyl and isopropyl
provided that at least one of R₁ and R₂ is t-butyl, t-amyl, or isopropyl, or a compound
of the formula:
where R₁ and R₂ are independently selected from hydrogen, t-butyl, t-amyl and isopropyl
provided that at least one of R₁ and R₂ is t-butyl, t-amyl, or isopropyl.
5. The concentrate of any of claims 1-3 wherein the phenol is a p-alkylphenol, and
the Mannich Base comprises N,N-dimethyl-N′-[2-hydroxy-5-dodecylbenzyl]-1,3-diaminopropane.
6. The concentrate of claim 2 wherein the metal deactivator is N,N′-disalicylidene-1,2-propylenediamine
and the Mannich Base is the reaction product of formaldehyde, 2,6-di-t-butyl phenol
and an amine selected from 1,3-diaminopropane, 1,2-diaminopropane, mixed C₁₂-C₁₄ t-alkyl
amines, and dimethylamine.
7. The concentrate of claim 2 wherein the metal deactivator is N,N′-disalicylidene-1,2-propylenediamine
and the Mannich Base is the reaction product of formaldehyde, p-dodecyl phenol, and
N,N-dimethyl-1,3-diaminopropane.
8. A fuel composition comprising middle distillate fuel containing from 3 to 1500
mgs/liter of the concentrate of any of claims 1-7.
9. A fuel composition comprising a middle distillate fuel and from 1 to 1400 mgs/liter
N,N-dimethylcyclohexylamine, from 0 to 400 mgs/liter N,N-di(ortho-hydroxyarylidene)-1,2-alkylenediamine
and from 1 to 1100 mgs/liter of a Mannich Base which is the reaction product of an
aldehyde, an amine and an alkyl phenol selected from (a) hindered phenol having the
formula:
where R₁, R₂, R₃ are independently selected from hydrogen, t-butyl, t-amyl and isopropropyl,
provided that at least one of R₁, R₂ and R₃ is hydrogen and at least one of R₁ and
R₂ is t-butyl, t-amyl or isopropyl; and (b) p-alkyl phenol having the formula:
where R₄ is C₉ to C₃₀ alkyl.
10. The fuel composition of claim 9 wherein the aldehyde is formaldehyde and the amine
is selected from one or more of:
A. alkyl monoamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl and R₆ is selected from C₁ to C₁₄
alkyl and the group -(CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
B. alkyl diamines of the formula;
where R₅ is selected from H and C₁ to C₅ alkyl R₈ is C₁ to C₆ alkylene and A and
B are independently selected from H, C₁ to C₅ alkyl, monohydroxysubstituted C₁ to
C₅ alkyl, and the group (CH₂)n-OR₇ where n = 1 to 10 and R₇ is C₁ to C₂₀ alkyl,
C. ethylene polyamines of the formula;
H₂N(̵(CH₂)₂NH)̵nH
where n = 2 to 10, and
D. cyclic amines of the formula;
where n and m are independently intergers from 1 to 3, X is selected from CH₂, O,
S and NR₉ where R₉ is H, C₁ to C₁₀ alkyl, or the group (CH₂)n-NH₂ where n is 1 to 10.