Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~273;~(31
This invention relates to additives for diesel
fuel oil.
Diesel fuel oil produces deposits in the injector
nozzles of diesel engines when burnt, which may cause clog~ing
of the injector nozzles. Hitherto, diesel fuel oil has
only rarely been supplemented with an addi-tive, but the
following prior art is known which discloses means for
cl~aning diesel engines.
Japanese Patent Publication No. 20550 of 1966
proposed a method which adds alkylphenol and oil-soluble
alkali or alkaline earth metal compounds to diesel fuel
oil for decreasing black smoke produced in the exhaust
gas when the diesel fuel oil is burnt. However, this method
is not effective in preventing the formation of deposits
in the injector nozzle of a diesel engine and the eventual
clogging thereo~.
U.S. Patent No. 4,409,000 describes a method
which enables an oxyalkylene compound of an amine to coexist
with hydrocarbon-soluble carboxylic dispersants, such as
an alkenylsuccineimide compound, by adding a volatile fuel
oil such as gasoline in order to keep clean a carburetor.
The combination of these compounds, however, cannot prevent
deposit in and clogging of the injector nozzle of a diesel
engine.
It is an object of the present invention to provide
an additive for diesel fuel oil which permits easy cleaning
and removal of deposits in the injector nozzles of diesel
engines.
According to the present invention, there is
provided a diesel fuel oil additive comprising
(A) an oxylakylene derivative of an amine having
the general formula:
R -N ~ 1 ----.... (1)
wherein Rl is an aliphatic hydrocarbon group having from
6 to 24 carbon atoms, Al is an alkylene group having
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from 2 to 4 carbon atoms, Q and m are integers of 1 or
more, with Q ~ m being a total of from 2 to lO; and
~B) a polyoxyalkylene glycol mono-ether having
the general formula:
~3-o-~A2o ~ H ....................... (2)
wherein R3 ls a hydrocarbon group having from 3 to 18 carbon
atoms, A2 is an alkylene group having 3 or 4 carbon atoms
and n is an integer of from 2 to 60.
This additive is added to the diesel fuel oil
directly or dissolved in a solvent.
The aliphatic hydrocarbon group having from 6
to 24 carbon atoms and represented by Rl in general formula
(l) includes linear or branched alkyl groups, such as hexyl,
heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl,
hexadecyl, octadecyl, eicosyl, and docosyl, and alkenyl
-~ groups, such as myristoleyl, palmitoleyl, oleyl, and linoleyl.
Among these, aliphatic hydrocarbons having from 8 to 20
carbon atoms are preferred with the decyl, dodecyl, tetradecyl,
hexadecyl, octadecyl, and oleyl groups being particularly
preferred. When Rl contains less than 5 or more than 25
carbon atoms, the effect on deposit removal is poor.
Suitable alkylene groups having from 2 to 4 carbon
atoms and represented by Al include ethylene, propylene,
butylene, and combinations of these groups, for example,
;; ethylene and propylene groups.
Each of Q and m represent an integer of 1 or
more, and Q + m is from 2 to lO, preferably from 2 to 4.
- When the value of Q + m is smaller than 2 or larger than
lO, the effect on deposit removal is poor.
Examples of oxyalkylene derivatives of an amine
of formula (1) are N,N-dihydroxyethyldodecylamine, N,N-
di-(hydroxyethoxyethyl) dodecylamine, N,N-dihydroxyethyl-
~' tetradecylamine, N,N-dihydroxyethylstearylamine, and N,N-
dihydroxyethyloleylamine.
In general formula (2) showing the polyoxyalkylene
- ~ glycol monoether (8) used in the invention, the hydrocarbon
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group having from 3 to 18 carbon atoms and represented
by R3 includes linear and branched alkyl groups such as
propyl, butyl, amyl, hexyl~ octyl, decyl, dodecyl, tridecyl,
tetradecyl, and hexadecyl, as well as phenyl groups having
an alkyl substituent, for example, butylphenyl, hexylphenyl,
octylphenyl, nonylphenyl, and dodecylphenyl groups. Among
these, hydrocarbon groups having from 3 to 12 carbon atoms
are preferred, and particularly preferred are propyl, butyl,
amyl, hexyl, octyl, and decyl groups. When R3 has less
than 3 or more than 18 carbon atoms, the effect on:deposit
removal is poor.
The alkylene group having 3 or 4 carbon atoms
and represented by A2 includes the propylene group and
~- 1,2-, 2,3-, 1,3-,;and 1,4- butylene groups, and combinations
of these groups. Among these, propylene is preferred.
Symbol n is an integer of from 2 to 60, preferably
from 4 to 45. When n is less than 2 or more than 60, the
effect on deposit removal is poor.
Specific examples of compounds represented by
20 the general formula (2) are a mono-n-propyl ether of poly- -
propylene glycol (average molecular weight: 600), a mono-
n-butyl ether of polypropylene glycol (average molecular
~;weight: 1700), a mono-2-ethylhexyl ether of polypropylene
glycol (average molecular weight: 14000), a mono-isodecyl
ether of polypropylene glycol (average molecular weight:
1200), and a mono-nonylphenol ether of polypropylene glycol
laverage molecular weight: 820).
The quantity by weight of additives (A) and (B)
used according to the invention ~an be selected as desired, but
the proportion of (A) is usually from 1 to 99% and that of (B) i5 from 99 to
1% based on the total weight of (A) plus (B); preferably from 10 to 99~ for
(A) and from 90 to 10% for (B)
The mixture of (A) and (B) can be diluted with
i~a suitable solvent to facilitate handling. Diluents available
,,,, 35 include general fuel oil (such as kerosine, gas oil, and
fuel oll), organic solvents readily miscible with petroleum
fuel oil (e.g. aromatic solvents such as benzene, toluene,
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1273, ~(31
and xylene and alcoholic solvents such as isopropanol,
butanol, and butyl cellosolve), and mixtures of two or
more of these solvents. Among these, toluene, xylene,
propanol, and butanol are preferred. The quantity of the
solvent to be used for dilution is usually from 0.1 to
100 parts by weight, preferably from 0.2 to 20 parts by
weight based on one part by weight of the mixture of ~A)
and (B).
The additives according to the invention can
be mixed with various other additives (such as antioxidants,
rust inhibitors, anticorrosive agents, fluidity improvers,
draining agents, cetane improvers, color stabilizers, clari-
fiers, detergent-dispersants, and bacteriostatic agents).
The diesel fuel oil used in conjunction with
the additives of the invention is a petroleum product used
for diesel engines, typified by kerosine (No. 1 and No.
2, JIS K-2203), gas oil (No. 1 to 3, Special No. 1 to 3,
~ JIS K-2204), and fuel oil A (JIS K-2205).
-~ The content of the additive according to the invention to be added to diesel fuel oil is normally from
0.001 to 5% by weight, preferably from 0.05 to 2% by weight
based on the weight of the fuel oil.
There is no particular restriction on the method
of addin~ the additive of the invention to diesel fuel
oil. For example, the additive can be directly added to
~ diesel fuel oil or can be diluted with a general fuel oil
; or aromatic hydrocarbon solvent before addition.
The additive according to the invention is readily
dissolved in diesel engine fuel oil and has no adverse
effect on various metals and resins used in the fuel system
of a diesel engine. Thus, it can be added directly or
be diluted with a solvent for addition to diesel fuel oil
in the fuel tank of a diesel car.
The additive dissolved in the fuel oil readily
cleans up deposits produced in the injector nozzle when
the engine is operated under normal conditions, thus pre-
venting the nozzle from plugging with the deposits.
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The additive of the invention further has the
effect of improving low temperature fluidity of diesel
fuel, of water draining, and of cleaning diesel engines,
and fuel systems.
The following non-limitative Examples illustrate
the invention, all percentages being by weight.
Example 1
A mixture of 40% of N,N-dihydroxyethyldodecylamine
and 60~ of an n-butyl ether of polypropylene glycol (number
average molecular weight: 1,800).
Example 2
A mixture of 10% of an N,N-dihydroxyethylated
derivative of hydrogenated tallow amine, 40~ of a mono-
n-butyl ether of polypropylene glycol (number average molecular
weight: 1,100) and 50~ xylene.
Control 1
A mixture of 40% of N,N-dihydroxyethyldodecylamine,
as mentioned in Example 1, and 60~ of a succinimide type
dispersant (Lubrizol 8~4 made by Lubrizol Co.: a reaction
produce of polyisobutene (molecular weight 1050), maleic
anhydride, and tetraethylenepentamine)).
Test Example 1
The performance of cleaning up deposits in the
nozzle of the injector of a diesel engine was tested on
the additives of the invention in Examples 1 and 2 and
on the additive in Control 1, by the following method:
Injector nozzles which were clogged by the attachment
of deposits by an actual run were mounted on a diesel engine,
and the engine was put to practical running for 2 hours
by use of a diesel fuel oil on the market added with the
additive of Examples 1 and 2 and in Control 1 to a concentration
~ of from zero to 1.0%, under conditions corresponding to
- a practical run at 60 km~hr, to clean the deposit.
The flow rate at the nozzle when the needle lift
was 0.1 to 0.5 mm was measured on the injector nozzle before
and after cleaning by the air flow method. The capacity
of cleaninq uP the deposit in the nozzle was compared by
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calculating the ratio of the nozzle flow rate to that of
a new nozzle measured in advance.
The cleaning test results of the injector nozzle
by the above method are shown in Table l.
Table l
Additive~ olume ad~ed¦Ratio of nozzle flow rate (~
¦t~ O lmm li~t10.35mm lift10. mm i t
A~r.......................... 1 24 1 40
c eanlng test:
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-----T-- ~O 20 25 40
Examp e .
~: 15 l ~.0 85 93 95
Exam~le
' ~ 56
~ Note l: The amount of additive added to the diesel fuel oil
'; is indicated by % by weight.
; Note 2: Indicated by:
Nozzle flow rate before or after cleaning test x lO0
Nozzle flow rate of new injector nozzle
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