CA1340601C - Diesel fuel compositions - Google Patents
Diesel fuel compositionsInfo
- Publication number
- CA1340601C CA1340601C CA000567798A CA567798A CA1340601C CA 1340601 C CA1340601 C CA 1340601C CA 000567798 A CA000567798 A CA 000567798A CA 567798 A CA567798 A CA 567798A CA 1340601 C CA1340601 C CA 1340601C
- Authority
- CA
- Canada
- Prior art keywords
- ammonium
- use according
- acid
- sulphate
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
- C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
Abstract
A diesel fuel composition containing a diesel fuel and a minor proportion by weight of a quaternary ammonium salt soluble therein. The quaternary ammonium salt is effective in reducing fouling of injector nozzles and in improving combusion chamber and piston cleanliness of diesel engines.
Description
1~40~~1 ,l_ pIEBEL FUEL C~OMpOSITInN
This invention concerns a diesel fuel having a reduced tendency to form deposits in and around the combustion chambers of diesel engines.
oxidation of fuel and incomplete Combustion results fn deposition of highly carbonaceous material in and around the combustion chambers of internal combustion engines.
First, excessive deposits around the tip of fuel injectors in indirect injection diesel engines can impair engine performance leading to poor startability, power reduction, higher noise, higher fuel consumption, etc.. Second, deposits around the pistons can lead to ring sticking, bore polishing, etc. leading to power reduction, high oil consumption, high emissions, etc.. In recent years these problems have become important because of the increasing use of i»direct injection die$el engines in passenger cars particularly those operating at high speeds.
It is therefore desirable to reduce deposits to accept2~ble levels which do not result in impaired performance: Many products are known to reduce injector deposits when added to the fuel, whilst claims have also been made on general combustion chamber cleanliness.
We have now found that the tendency of diesel fuels to form deposits in and around the combustion chambers of the indirect injection diesel engines may be significantly reduced by incorporating in the fuel a quaternary ammonium compound. There exist several patents dating back to the 1950'x, 1960~s and early 1970's (f.e. prior to the development of the high speed diesel engines) which propose the addition of quaternary ammonium compounds to distillate fuels for various functions although there is no suggestion that the addition of suvh compounds) will reduce the formation of deposits due to incomplete fuel combustion in and around combustion chambers.
Examples of such patents include U.S. Patent No 3158647 which disclases the use of quaternary ammonium fatty acid, phenate, and naphthenate salts in the stabilisation of distillate fuel oils. This patent relates to the problem of sludge deposition in distillate fuel oil during storage at ambient temperatures and the problem of sludge deposits causing clogging of burnex filters etc.. This patent does not concern the formation of deposits in and around the combustion chambers of diesel engines.
U.S. Patents No. 3408813 and 3346353 concern a petroleum distillate fuel containing an ashless oil soluble polymeric dispersant stabilising additive and a diaikyl dimethyl ammonium chloride or a dialkyl dimethyl au~monium nitrite, respectively) These additives are adapted to prevent the formation of persistent haze and stable emulsions when the petroleum distillate fuel is contacted with water during handling and storage.
,.
This invention concerns a diesel fuel having a reduced tendency to form deposits in and around the combustion chambers of diesel engines.
oxidation of fuel and incomplete Combustion results fn deposition of highly carbonaceous material in and around the combustion chambers of internal combustion engines.
First, excessive deposits around the tip of fuel injectors in indirect injection diesel engines can impair engine performance leading to poor startability, power reduction, higher noise, higher fuel consumption, etc.. Second, deposits around the pistons can lead to ring sticking, bore polishing, etc. leading to power reduction, high oil consumption, high emissions, etc.. In recent years these problems have become important because of the increasing use of i»direct injection die$el engines in passenger cars particularly those operating at high speeds.
It is therefore desirable to reduce deposits to accept2~ble levels which do not result in impaired performance: Many products are known to reduce injector deposits when added to the fuel, whilst claims have also been made on general combustion chamber cleanliness.
We have now found that the tendency of diesel fuels to form deposits in and around the combustion chambers of the indirect injection diesel engines may be significantly reduced by incorporating in the fuel a quaternary ammonium compound. There exist several patents dating back to the 1950'x, 1960~s and early 1970's (f.e. prior to the development of the high speed diesel engines) which propose the addition of quaternary ammonium compounds to distillate fuels for various functions although there is no suggestion that the addition of suvh compounds) will reduce the formation of deposits due to incomplete fuel combustion in and around combustion chambers.
Examples of such patents include U.S. Patent No 3158647 which disclases the use of quaternary ammonium fatty acid, phenate, and naphthenate salts in the stabilisation of distillate fuel oils. This patent relates to the problem of sludge deposition in distillate fuel oil during storage at ambient temperatures and the problem of sludge deposits causing clogging of burnex filters etc.. This patent does not concern the formation of deposits in and around the combustion chambers of diesel engines.
U.S. Patents No. 3408813 and 3346353 concern a petroleum distillate fuel containing an ashless oil soluble polymeric dispersant stabilising additive and a diaikyl dimethyl ammonium chloride or a dialkyl dimethyl au~monium nitrite, respectively) These additives are adapted to prevent the formation of persistent haze and stable emulsions when the petroleum distillate fuel is contacted with water during handling and storage.
,.
U.S. Patent No 3397970 relates to a petroleum distillate oil containing a pour point depressing amount of a copolymer of ethylene and an olefinicaliy unsaturated aliphatic ester monomer (for example vinyl acetate) ~aaid copolymer tending to promote the formation of water haze in said oil, and as an inhibitor of said haze a dimar of linoleic acid and quaternary ammonium salt selected from dicocyl dimethyl ammonium chloride and dicocyl dimethyl ammonium nitrite.
U.S. Patent No 3493354 disoloses a diesel fuel addit.~ve containing a mayor amount of an organic barium compound in combination with a minor amount of a quaternary ammonium salt. The additive promotes the combustion of the fuel, thereby reducing the proportion of unburned hydrocarbons and suspended soot particles in the exhaust gases of diesel engines. The quaternary ammonium salts serves to prevent the extraction of barium by water with which the additive or fuel containing the additzve may come into contact.
United Kingdom Patents 973826 and 1076497 relate to using quaternary ammonium compounds, particularly nitrates as distillate fuel stabilisers whereas United Kingdom Patent 1432265 proposes their use as antistatic agents together with polysulphones.
It is one object of the present invention to reduce the levels of deposits formed in and around the combustion chambers of diesel engines to acceptable levels withour impairing performance. It is a further object of the present invention to produce an improved diesel fuel compos it~.on .
~~4000~
According to our invention a diesel fuel composition for use in an indirect injection engine comprises a diesel fuel and a minor proportion by weight of a quaternary ammonium salt soluble therein.
Thus, the present invention relates to the use of a minor proportion by weight of a quaternary ammonium salt soluble in a diesel fuel for use in an indirect injection diesel engine.
The four residues connected to the quaternary nitrogen atom of the quaternary ammonium salt are essentially hydrocarbyl residues. These residues may be similar or dissimilar. They may be substituted with functional groups or have incorporated therein functional groups as parts of the hydrocarbyl chain.
Usually one or two of these residues contain at least 6 carbon atoms while the remaining residues contain less than 6 carbon atoms. It is preferred that one of the residues contains at least 8 carbon atoms while the remaining residues contain less than 6 carbon atoms.
Usually the hydrocarbyl residues are alkyl groups, alkenyl groups, aryl groups or alkaryl groups. Examples of alkyl groups containing less than 6 carbon atoms are methyl, ethyl, isopropyl, propyl and butyl groups. Examples of alkyl groups containing more than 6 carbon atoms are dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (cetyl) and octadecyl (stearyl) groups. Examples of alkenyl groups containing more than 6 carbon atoms are dodecynyl, tetradecenyl, octadecenyl (oleyl), and octadecadienyl (linoleyl) groups. The residues containing more than 6 carbon atoms can be derived from natural fats and oils, -5~
for example coconut oil, eoya bean oil; animal tallow and the like. In such instances thesA residues will consist essentially of mixod alkyl groups containing 8 to 22 carbon atoms.
As mentioned above, the hydrocarbyl residues may contain functional groups. Examples o! functional groups which may be present in the residues are hydroxy, halide, ester, amide, ether, amine, and sulphide functions.
It is preferred that the anionic radical is a strong acid radical. Examples of strong acid radicals u$eful according to the invention are nitrate, sulphate) ethosulphate, sulphonate (both alkyl and elkyl$ry~.)~ sulphurised phenate, carboxylate, and borate. It is also possible to employ mixtures of anionic radicals.
when the quaternary ammonium compound is a sulphanate it can be made from:
(1) Alkylbenzene-sulphonic acids or alkyinaphthalene-sulphonic acids examples of which include Benzene-sulphonic acids with straight-chain or branched single or multiple substituted alkyl radicals with 4-24 (preferably s-20) carbon atoms in the aromatic nucleus, for example dodecyl-benzene-sulphonic acid, dinonylbenzene-sulphonic acid, dadecylnaphthalenesulphonic acid etc.
-6- l3~Ob0~
(2) Alkane-sulphonic acids including Sulphonic acids possessing straight-chain or branched alkyl radicals usually with 10-30 carbon atoms, for example tetradecyl sulphonic acid etc.
(3) Alkene-sulphonic acids including Sulphonic acids which have straight-chain or branched alkenyl radicals usually with 15-30 carbon atoms, for example 2-eicosenyl sulphonic acid etc.
The sulphonic acids are typically obtained by sulphonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of an aromatic hydrocarbon, for example, benzene, toluene, xylene, naphthalene, diphenyl. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 30 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, polyolefins, or, for example, polymers of ethylene, propylene, butene, etc. The alkaryl sulphonates usually contain from about 9 to about 20 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl substituted aromatic moiety.
~3~o~oZ
_, _ Quaternary ammonium gulphurfsed phenates ors synthesised from sulphurised alkylphenola which have the general structure:
OH ON
,~ S~
R R R
where R is an alkyl radical, n is an integer from 0 to 4 and x is an integer from 1 to 4. The average number of carbon atoms in all of the R groups is preferably at least about 9 in order to ensure adequate solubility in oil. The individual R groups may contain from 5 to 40, preferably s to 20 carbon atoms. Alkylation of phenol may be carried out with alkylating agents of the types used to alkylate aromatic hydrocarbons in the manufacture of alkaryl sulphonates. Sulphurisation may be by reaction of the alkyl phenol with sulphur chloride or by reaction with sulphur. In the latter case, the alkyl phenol is usually present as the metal salt, although other sulphurisation promoters may be used, such as amines.
Quaternary ammonium carboxylates are synthesised from:
1 ~~ ono ~
-g-(i) Monocarboxylia acid$ including (a) Aliphatic monocarboxylic acids possessing saturated ox unsaturated straight or branched chains usually with 0-6 carbon atoms, for example, formic acid, ac~atic acid, prapionic acid, butyric acid, valeric acid, caproic acid.
(b) Aromatic monocarboxylic acids with single or multiple substituted hydrocarbon xadicals possessing saturated or unsaturated straight or branched Chains usually with 0-35 (preferably 0-24) carbon atoms in the aromatic nucleus, far example, benzo~.c acid, 0-toluic acid, m-toluic acid, p-toluic acid, p-actylbenzaic acid, p-nonylben2oic acid, dibutylbenzoic acid, salicylic acid, methyl salicylic acid, ethyl salicylic acid, octylsalicylic acid, nonylsalicylic acid, dodecylsalicylic acid, tetradecylsalicylic acid, octadecylsalicylic acid etc.
(2) Polycarboxylic acids including (a) Aliphatic palycarboxylic acids possessing saturated or unsaturated straight or branched Chains usually with 0-80 (preferably 0-50) carbon ~~40a0L
'9-atoms, for example oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, axelaic acid, sebacic acid, maleic acid, fumaric acid, tricarballylic acid, polymeric fatty acids (dimeric acid, trimeric acid etc.), alkenyl succinic acids (such as polyisobutenylsuccinic acid), or the anhydrides of such polycarboxylic acids.
(b) Aromatic polycarboxylic acids with single or multiple substituted hydrocarbon radicals possessing saturated or unsaturated straight or branched chains usually with 0-35 (preferably 0-24) carbon atoms in the aromatic nucleus, for example phthalic acid, iso~phtbalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimeric acid; methyl phthalic acid, dodecylphthalic acid etc.
Preferred among the carboxylic acids are the simple monocarboxylic acids (such as formic acid and acetic acid), and the simple dicarboxylic acids (such as oxalic acid).
Many of the quaternary ammonium salts which may be employed according to the present invention are commercially available. It is preferred to use one of those readily available compounds. Alternatively the quaternary ammonium compounds can be synthesised in any suitable manner. Since the method of preparing the quaternary ammonium compounds is not part of the invention, the preparation of the compounds will nat be described in detail. It should 1~40~i01 --lo-be noted, however, that we have two preferred methods for the synthesis of compounds such as guaternary ammonium sulphonates, sulphurised phenates and carboxylates.
In the first method a quaternary ammonium hydroxide is prepared by reacting a guaternary ammonium halide (for example the chloride) with stn alkali metal hydroxide (tor example sodium hydroxide) in an alcohol (for example methanol).
[ R4 N ] ( + ) X ( ~ ? + NaOH -~--~-~-r-s' ( R4 N ] ( + ) OI~i W ) + NaX
After removing the metal halide by filtration the solution of quaternary ammonium hydroxide is mixed with the acid HA
where A is the desired anion in a suitable solvent and allowed to react:-[R4N](+) OH(-) + HA (R4N](+) A(-) + HZO
The rate of reaction may be increased by raising the reaction temperature above the ambient temperature. Once the reaction is complete the solvents and water are removed by distillation.
In the second method the organic acid HA is reacted with a metal oxide or hydroxide to form the metal salt:
HA + NaOH ----~ NaA + I~20 If the reaction is done in a suitable solvent (for example heptane or toluene) the water formed during the reaction may be removed by refluxing the solvent and using a Dean and Stark trap. Once all the water has been rempved the solution of the metal salt is treated with a quaternary ammonium halide:
~~~ooo~
NaA + (R4NJ(+)C1(-) --~ (R4NJ(+)A(-) + NaCl The metal halido is removed by filtration and the solvant is removed by distillation. Alternatively, the solvent can be removed by distillation and the metal halide filtered from the final product.
The amount of quaternary ammonium salt which is added to the diesel fuel is a minor proportion by weight preferably less than l wt.$ and mo&t preferably 0.000001 to 0.1 wt.$
especially 2 to 200 ppm.
Other additive materials commonly usad in diesel fuel may also be included in the diesel fuel compositions according to the present invention. Such other additive materials may comprise corrosion inhibitors, dyes and the like) The effect of quaternary ammonium salts employed according to the present invention on the fouling of injector nozzles and combustion chamber and piston cleanliness of diesel engines is illustrated by the following specific examples in which the following compounds are employed:
Di(2-hydroxyethyl) ethyl octadecenyl ammonium etho-sulphate (compound A) GHz - GHa ~ ~H
//
GHQ--CGN~,~ CH = GN tGH~,~ -- ~ - ~N~- GHj ~- l! or~Nz~GN3.
G N~, -GNi - oN
~340~~1 -lZ_ cetyltrimethyl ammonium sulphonate (compound 8) ~s t~ ~ _ ~~' H'~a N - GNa 4 -~ s --r ~N~ o Cetyltrimethyl ammonium nonylphenyl sulphide (compound C) cb N~~- N ~ GNP ~ I
G N,, x ~ ~N~~ GyH~, Dimethyl dodecyl ethyl z~mmonium etho-sulphate (compound D) G~a. ~s~~ '_"_ N~+~ ' CN CN 4 ' s --' O - GH 'G
GNP O
1~~~601.
~13-Dimethyl ethyl (3-atearyl amino propyl) ammonium etho-sulphate (compound E) O GHQ o G~ H,~e. ~,G - N1~I GHQ, ~- ~I~~ GH~,~ C.N~ ~O-- S-- O - GH,-GNP
il G N, O
Dimethyl ethyl (3-lauryl amino propyl) ammonium etho-sulphate (Compound F) G N~
C« N~~ - G - NH - ~Gl~~,~j - N ~ GNx~GN3 , p - ~ --d - GEC-GHQ
car, d Dicocodimethyl ammonium formats (Campouhd G) Dicocodimethyl ammonium borate (Compound H) Dicocodimethyl ammonium nonyl phenyl sulphide (Compound I) Dicocdimethyl ammonium oxalate (Compound J) GNP
r (~
G« N~5 ' N '~ ~rz~~5- ~~1 ooc. .- Gd o~
i w. GNP ..
134Q~;0~
The effectiveness of quaternary ammonium salt additives on the coking of injector nozzles in diesel engines was determined using a Fiat Ritmo engine having the following specification.
Number of Cylinders 4 in line speed 4500 rpm Maximum Power 42.66 kw Bore 83 mrn Stroke 79.2 mm Displacement 1.714 litres Compression Ratio 20.5:1 Oil Volume 5.0 litres In the tests the engine is run for 60 twenty u~inute cycles to simulate the urban driving cycle. Each cycle consists of four minute periods as follows:
(a) 1000 rpm idle 0 BHP 0 Load (b) 3000 rpm 65% potential speed 27 BHP 40-~45% Max Load (c) 1600 rpm 35% potential speed ?.2 BHP 35-40% Max Load (d) 4200 rpm 90% potential speed 42 BHP 70-8-% Max Load Before and after the engine test the injectors were rated according to the test method of ISO 4010. This test works on the principle of a vacuum being maintained across the injector at a specific needle lift. Tn order to maintain this vacuum at the desired level the air-flow into the n ~34a~0~
injector may vary. This air-flow into the injector is recorded. The air-flow into the injector becomes less as the injectors become coked. The results are recorded as the difference between clean and dirty, i.e. before and after tests air-flow. The formula used is as follows:
Percent Air Flow = Before Test - After Test x 100 Loss Before Test In this and the following examples the results presented are the averages of four results at one specific setting of the injectors (0.1 mm lift) .
The diesel fuel used in Example 1 was a diesel fuel obtained from Italy. The compound according to the present invention tested in this diesel fuel was Compound A. A comparative test has been carried ut using a typical product already being sold for injector nozzle cleanliness application (commercial product). This is an additive of the type described in the EP
Patent No. 0,203,692. It is a mixture of a phenol compound and a cyclic amide derived from dicarboxylic acid or anhydride.
The results obtained are shown in Table I, attached.
~~~o~~~
Examcl~
Th8 ~ftertiEanB~g~Rf ~~t~R~n3~_~t~onium__~alt~_according to engines was determined using a Fiat Regata engine having the following specif ioation.
Humber of Cylinders 4 in line Speed 4600 rpm Maximum Power 48.00 kw Bore 82.60 mm stroke 90.00 mm Displacement 1.92 litres Compression Ratio 21:1 Oil Volume 5.7 litres In the test the engine way x"un for 60 twenty-minute cycles to simulate the urban driving cycle.
The total duration of 20 hours represents 1,600 km (1,000 miles) of city driving conditions.
Each cycle consisted of four five minute periods as follows:
(a) 1100 rpm idle o BHP 0 Load (b) 3120 rpm 65% potential speed 21.1 BHP 40-45% Max Load (c) 1680 rpm 35% potential speed 9.4 BHP 35-40% Max Load (d) 4320 rpm 90% potential speed 45.4 BHP 70-80% Hax Load l~~OnOI
Further test conditions were as lollcws:-Manifold Air Temperature 26t 2oC
Coolant Outlet 92t 2oC
coolant Temperature difler~nce s-6oC
oil Temperature at 3000 rpm iiot 2oC
Fuei Temperature 48~ 2oC
Exhaust Temperature at 300 rpm 3o0aC
Various aompound~ according to the present invention were tested in a UK commercial diesel fuel and the results obtained are presented in Tab7~.e II.
Examp a 3 The tests in this example have been carried out as described for Example Z. Ag$in, a UK commercial diesel fuel has been employed. A comparative result obtained with the commercial additive product mentioned in Example 1 is included in the attached Table III.
The compounds according to the present invention tested in this example are set out in Table 3.
.~3~0001 ANTI-COKING PERFORMANCE IN FIAT RITMO ENGINE TEST
Fuel %FL~W ~OS,~
Base Italian diesel 71.0 Base + 40 ppm or commercial product 44.7 Base 37.5 ppm of compound A 10.0 Fuel % Flow Redaction Base UK commercial diesel 65-70 (in repeat tests) Base + 25 ppm of compound H 48.3 Base + 25 ppm of col~poundC 46.9 Base + 37.5 ppm of compound G 27.0 Base + 3?.5 ppm of compound H 26.8 Base + 37.5 ppm of compound I 8.1 Base + 37.5 ppm of compound J 5.0 ~3~0~0~
glow ~eduotion Base UK Commercial Diesel Base 40 ppm of commercial product + 70 Base 50 ppm of compound D 22.7 +
Base 100 ppm of compound D 15.4 +
Base 50 ppm of compound E 20.5 +
U.S. Patent No 3493354 disoloses a diesel fuel addit.~ve containing a mayor amount of an organic barium compound in combination with a minor amount of a quaternary ammonium salt. The additive promotes the combustion of the fuel, thereby reducing the proportion of unburned hydrocarbons and suspended soot particles in the exhaust gases of diesel engines. The quaternary ammonium salts serves to prevent the extraction of barium by water with which the additive or fuel containing the additzve may come into contact.
United Kingdom Patents 973826 and 1076497 relate to using quaternary ammonium compounds, particularly nitrates as distillate fuel stabilisers whereas United Kingdom Patent 1432265 proposes their use as antistatic agents together with polysulphones.
It is one object of the present invention to reduce the levels of deposits formed in and around the combustion chambers of diesel engines to acceptable levels withour impairing performance. It is a further object of the present invention to produce an improved diesel fuel compos it~.on .
~~4000~
According to our invention a diesel fuel composition for use in an indirect injection engine comprises a diesel fuel and a minor proportion by weight of a quaternary ammonium salt soluble therein.
Thus, the present invention relates to the use of a minor proportion by weight of a quaternary ammonium salt soluble in a diesel fuel for use in an indirect injection diesel engine.
The four residues connected to the quaternary nitrogen atom of the quaternary ammonium salt are essentially hydrocarbyl residues. These residues may be similar or dissimilar. They may be substituted with functional groups or have incorporated therein functional groups as parts of the hydrocarbyl chain.
Usually one or two of these residues contain at least 6 carbon atoms while the remaining residues contain less than 6 carbon atoms. It is preferred that one of the residues contains at least 8 carbon atoms while the remaining residues contain less than 6 carbon atoms.
Usually the hydrocarbyl residues are alkyl groups, alkenyl groups, aryl groups or alkaryl groups. Examples of alkyl groups containing less than 6 carbon atoms are methyl, ethyl, isopropyl, propyl and butyl groups. Examples of alkyl groups containing more than 6 carbon atoms are dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (cetyl) and octadecyl (stearyl) groups. Examples of alkenyl groups containing more than 6 carbon atoms are dodecynyl, tetradecenyl, octadecenyl (oleyl), and octadecadienyl (linoleyl) groups. The residues containing more than 6 carbon atoms can be derived from natural fats and oils, -5~
for example coconut oil, eoya bean oil; animal tallow and the like. In such instances thesA residues will consist essentially of mixod alkyl groups containing 8 to 22 carbon atoms.
As mentioned above, the hydrocarbyl residues may contain functional groups. Examples o! functional groups which may be present in the residues are hydroxy, halide, ester, amide, ether, amine, and sulphide functions.
It is preferred that the anionic radical is a strong acid radical. Examples of strong acid radicals u$eful according to the invention are nitrate, sulphate) ethosulphate, sulphonate (both alkyl and elkyl$ry~.)~ sulphurised phenate, carboxylate, and borate. It is also possible to employ mixtures of anionic radicals.
when the quaternary ammonium compound is a sulphanate it can be made from:
(1) Alkylbenzene-sulphonic acids or alkyinaphthalene-sulphonic acids examples of which include Benzene-sulphonic acids with straight-chain or branched single or multiple substituted alkyl radicals with 4-24 (preferably s-20) carbon atoms in the aromatic nucleus, for example dodecyl-benzene-sulphonic acid, dinonylbenzene-sulphonic acid, dadecylnaphthalenesulphonic acid etc.
-6- l3~Ob0~
(2) Alkane-sulphonic acids including Sulphonic acids possessing straight-chain or branched alkyl radicals usually with 10-30 carbon atoms, for example tetradecyl sulphonic acid etc.
(3) Alkene-sulphonic acids including Sulphonic acids which have straight-chain or branched alkenyl radicals usually with 15-30 carbon atoms, for example 2-eicosenyl sulphonic acid etc.
The sulphonic acids are typically obtained by sulphonation of alkyl substituted aromatic hydrocarbons, such as those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of an aromatic hydrocarbon, for example, benzene, toluene, xylene, naphthalene, diphenyl. The alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 30 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, polyolefins, or, for example, polymers of ethylene, propylene, butene, etc. The alkaryl sulphonates usually contain from about 9 to about 20 or more carbon atoms, preferably from about 16 to about 50 carbon atoms per alkyl substituted aromatic moiety.
~3~o~oZ
_, _ Quaternary ammonium gulphurfsed phenates ors synthesised from sulphurised alkylphenola which have the general structure:
OH ON
,~ S~
R R R
where R is an alkyl radical, n is an integer from 0 to 4 and x is an integer from 1 to 4. The average number of carbon atoms in all of the R groups is preferably at least about 9 in order to ensure adequate solubility in oil. The individual R groups may contain from 5 to 40, preferably s to 20 carbon atoms. Alkylation of phenol may be carried out with alkylating agents of the types used to alkylate aromatic hydrocarbons in the manufacture of alkaryl sulphonates. Sulphurisation may be by reaction of the alkyl phenol with sulphur chloride or by reaction with sulphur. In the latter case, the alkyl phenol is usually present as the metal salt, although other sulphurisation promoters may be used, such as amines.
Quaternary ammonium carboxylates are synthesised from:
1 ~~ ono ~
-g-(i) Monocarboxylia acid$ including (a) Aliphatic monocarboxylic acids possessing saturated ox unsaturated straight or branched chains usually with 0-6 carbon atoms, for example, formic acid, ac~atic acid, prapionic acid, butyric acid, valeric acid, caproic acid.
(b) Aromatic monocarboxylic acids with single or multiple substituted hydrocarbon xadicals possessing saturated or unsaturated straight or branched Chains usually with 0-35 (preferably 0-24) carbon atoms in the aromatic nucleus, far example, benzo~.c acid, 0-toluic acid, m-toluic acid, p-toluic acid, p-actylbenzaic acid, p-nonylben2oic acid, dibutylbenzoic acid, salicylic acid, methyl salicylic acid, ethyl salicylic acid, octylsalicylic acid, nonylsalicylic acid, dodecylsalicylic acid, tetradecylsalicylic acid, octadecylsalicylic acid etc.
(2) Polycarboxylic acids including (a) Aliphatic palycarboxylic acids possessing saturated or unsaturated straight or branched Chains usually with 0-80 (preferably 0-50) carbon ~~40a0L
'9-atoms, for example oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, axelaic acid, sebacic acid, maleic acid, fumaric acid, tricarballylic acid, polymeric fatty acids (dimeric acid, trimeric acid etc.), alkenyl succinic acids (such as polyisobutenylsuccinic acid), or the anhydrides of such polycarboxylic acids.
(b) Aromatic polycarboxylic acids with single or multiple substituted hydrocarbon radicals possessing saturated or unsaturated straight or branched chains usually with 0-35 (preferably 0-24) carbon atoms in the aromatic nucleus, for example phthalic acid, iso~phtbalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimeric acid; methyl phthalic acid, dodecylphthalic acid etc.
Preferred among the carboxylic acids are the simple monocarboxylic acids (such as formic acid and acetic acid), and the simple dicarboxylic acids (such as oxalic acid).
Many of the quaternary ammonium salts which may be employed according to the present invention are commercially available. It is preferred to use one of those readily available compounds. Alternatively the quaternary ammonium compounds can be synthesised in any suitable manner. Since the method of preparing the quaternary ammonium compounds is not part of the invention, the preparation of the compounds will nat be described in detail. It should 1~40~i01 --lo-be noted, however, that we have two preferred methods for the synthesis of compounds such as guaternary ammonium sulphonates, sulphurised phenates and carboxylates.
In the first method a quaternary ammonium hydroxide is prepared by reacting a guaternary ammonium halide (for example the chloride) with stn alkali metal hydroxide (tor example sodium hydroxide) in an alcohol (for example methanol).
[ R4 N ] ( + ) X ( ~ ? + NaOH -~--~-~-r-s' ( R4 N ] ( + ) OI~i W ) + NaX
After removing the metal halide by filtration the solution of quaternary ammonium hydroxide is mixed with the acid HA
where A is the desired anion in a suitable solvent and allowed to react:-[R4N](+) OH(-) + HA (R4N](+) A(-) + HZO
The rate of reaction may be increased by raising the reaction temperature above the ambient temperature. Once the reaction is complete the solvents and water are removed by distillation.
In the second method the organic acid HA is reacted with a metal oxide or hydroxide to form the metal salt:
HA + NaOH ----~ NaA + I~20 If the reaction is done in a suitable solvent (for example heptane or toluene) the water formed during the reaction may be removed by refluxing the solvent and using a Dean and Stark trap. Once all the water has been rempved the solution of the metal salt is treated with a quaternary ammonium halide:
~~~ooo~
NaA + (R4NJ(+)C1(-) --~ (R4NJ(+)A(-) + NaCl The metal halido is removed by filtration and the solvant is removed by distillation. Alternatively, the solvent can be removed by distillation and the metal halide filtered from the final product.
The amount of quaternary ammonium salt which is added to the diesel fuel is a minor proportion by weight preferably less than l wt.$ and mo&t preferably 0.000001 to 0.1 wt.$
especially 2 to 200 ppm.
Other additive materials commonly usad in diesel fuel may also be included in the diesel fuel compositions according to the present invention. Such other additive materials may comprise corrosion inhibitors, dyes and the like) The effect of quaternary ammonium salts employed according to the present invention on the fouling of injector nozzles and combustion chamber and piston cleanliness of diesel engines is illustrated by the following specific examples in which the following compounds are employed:
Di(2-hydroxyethyl) ethyl octadecenyl ammonium etho-sulphate (compound A) GHz - GHa ~ ~H
//
GHQ--CGN~,~ CH = GN tGH~,~ -- ~ - ~N~- GHj ~- l! or~Nz~GN3.
G N~, -GNi - oN
~340~~1 -lZ_ cetyltrimethyl ammonium sulphonate (compound 8) ~s t~ ~ _ ~~' H'~a N - GNa 4 -~ s --r ~N~ o Cetyltrimethyl ammonium nonylphenyl sulphide (compound C) cb N~~- N ~ GNP ~ I
G N,, x ~ ~N~~ GyH~, Dimethyl dodecyl ethyl z~mmonium etho-sulphate (compound D) G~a. ~s~~ '_"_ N~+~ ' CN CN 4 ' s --' O - GH 'G
GNP O
1~~~601.
~13-Dimethyl ethyl (3-atearyl amino propyl) ammonium etho-sulphate (compound E) O GHQ o G~ H,~e. ~,G - N1~I GHQ, ~- ~I~~ GH~,~ C.N~ ~O-- S-- O - GH,-GNP
il G N, O
Dimethyl ethyl (3-lauryl amino propyl) ammonium etho-sulphate (Compound F) G N~
C« N~~ - G - NH - ~Gl~~,~j - N ~ GNx~GN3 , p - ~ --d - GEC-GHQ
car, d Dicocodimethyl ammonium formats (Campouhd G) Dicocodimethyl ammonium borate (Compound H) Dicocodimethyl ammonium nonyl phenyl sulphide (Compound I) Dicocdimethyl ammonium oxalate (Compound J) GNP
r (~
G« N~5 ' N '~ ~rz~~5- ~~1 ooc. .- Gd o~
i w. GNP ..
134Q~;0~
The effectiveness of quaternary ammonium salt additives on the coking of injector nozzles in diesel engines was determined using a Fiat Ritmo engine having the following specification.
Number of Cylinders 4 in line speed 4500 rpm Maximum Power 42.66 kw Bore 83 mrn Stroke 79.2 mm Displacement 1.714 litres Compression Ratio 20.5:1 Oil Volume 5.0 litres In the tests the engine is run for 60 twenty u~inute cycles to simulate the urban driving cycle. Each cycle consists of four minute periods as follows:
(a) 1000 rpm idle 0 BHP 0 Load (b) 3000 rpm 65% potential speed 27 BHP 40-~45% Max Load (c) 1600 rpm 35% potential speed ?.2 BHP 35-40% Max Load (d) 4200 rpm 90% potential speed 42 BHP 70-8-% Max Load Before and after the engine test the injectors were rated according to the test method of ISO 4010. This test works on the principle of a vacuum being maintained across the injector at a specific needle lift. Tn order to maintain this vacuum at the desired level the air-flow into the n ~34a~0~
injector may vary. This air-flow into the injector is recorded. The air-flow into the injector becomes less as the injectors become coked. The results are recorded as the difference between clean and dirty, i.e. before and after tests air-flow. The formula used is as follows:
Percent Air Flow = Before Test - After Test x 100 Loss Before Test In this and the following examples the results presented are the averages of four results at one specific setting of the injectors (0.1 mm lift) .
The diesel fuel used in Example 1 was a diesel fuel obtained from Italy. The compound according to the present invention tested in this diesel fuel was Compound A. A comparative test has been carried ut using a typical product already being sold for injector nozzle cleanliness application (commercial product). This is an additive of the type described in the EP
Patent No. 0,203,692. It is a mixture of a phenol compound and a cyclic amide derived from dicarboxylic acid or anhydride.
The results obtained are shown in Table I, attached.
~~~o~~~
Examcl~
Th8 ~ftertiEanB~g~Rf ~~t~R~n3~_~t~onium__~alt~_according to engines was determined using a Fiat Regata engine having the following specif ioation.
Humber of Cylinders 4 in line Speed 4600 rpm Maximum Power 48.00 kw Bore 82.60 mm stroke 90.00 mm Displacement 1.92 litres Compression Ratio 21:1 Oil Volume 5.7 litres In the test the engine way x"un for 60 twenty-minute cycles to simulate the urban driving cycle.
The total duration of 20 hours represents 1,600 km (1,000 miles) of city driving conditions.
Each cycle consisted of four five minute periods as follows:
(a) 1100 rpm idle o BHP 0 Load (b) 3120 rpm 65% potential speed 21.1 BHP 40-45% Max Load (c) 1680 rpm 35% potential speed 9.4 BHP 35-40% Max Load (d) 4320 rpm 90% potential speed 45.4 BHP 70-80% Hax Load l~~OnOI
Further test conditions were as lollcws:-Manifold Air Temperature 26t 2oC
Coolant Outlet 92t 2oC
coolant Temperature difler~nce s-6oC
oil Temperature at 3000 rpm iiot 2oC
Fuei Temperature 48~ 2oC
Exhaust Temperature at 300 rpm 3o0aC
Various aompound~ according to the present invention were tested in a UK commercial diesel fuel and the results obtained are presented in Tab7~.e II.
Examp a 3 The tests in this example have been carried out as described for Example Z. Ag$in, a UK commercial diesel fuel has been employed. A comparative result obtained with the commercial additive product mentioned in Example 1 is included in the attached Table III.
The compounds according to the present invention tested in this example are set out in Table 3.
.~3~0001 ANTI-COKING PERFORMANCE IN FIAT RITMO ENGINE TEST
Fuel %FL~W ~OS,~
Base Italian diesel 71.0 Base + 40 ppm or commercial product 44.7 Base 37.5 ppm of compound A 10.0 Fuel % Flow Redaction Base UK commercial diesel 65-70 (in repeat tests) Base + 25 ppm of compound H 48.3 Base + 25 ppm of col~poundC 46.9 Base + 37.5 ppm of compound G 27.0 Base + 3?.5 ppm of compound H 26.8 Base + 37.5 ppm of compound I 8.1 Base + 37.5 ppm of compound J 5.0 ~3~0~0~
glow ~eduotion Base UK Commercial Diesel Base 40 ppm of commercial product + 70 Base 50 ppm of compound D 22.7 +
Base 100 ppm of compound D 15.4 +
Base 50 ppm of compound E 20.5 +
Claims (11)
1. Use in an indirect injection diesel engine for inhibiting coking of a diesel fuel composition containing from 0.000001 to 0.1 weight percent of a quaternary ammonium salt soluble therein.
2. The use according to claim 1 wherein the four residues connected to the quaternary nitrogen atom of said salt are independently selected from hydrocarbyl residues.
3. The use according to claim 2 wherein one or two of said residues contain at least 6 carbon atoms while the remaining residues contain less than 6 carbon atoms.
4. The use according to claim 3 wherein one of said residues contains at least 8 carbon atoms while the remaining residues contain less than 6 carbon atoms.
5. The use according to any one of claims 2, 3 or 4 wherein at least one of the hydrocarbyl residues contain at least one functional group as a substituent or as a member of the hydrocarbon chain.
6. The use according to any one of claims 2, 3 or 4 wherein said hydrocarbyl residues are selected from alkyl groups, alkenyl groups, aryl groups or alkaryl groups.
7 The use according to claim 5 wherein said functional group is selected from hydroxy, halide, carboxy, amide, ether, amine, and sulphide.
8. The use according to any one of claims 2, 3, or 4 wherein the anionic radical of the quaternary ammonium salt is a strong acid radical.
9. The use according to claim 8 wherein the anionic radical is nitrate, sulphate, ethosulphate, alkyl sulphate alkylaryl sulphonate, sulphurised phenate, carboxylate and borate, or any combination thereof.
10. The use according to claim 1 wherein the quaternary ammonium salt comprises one or more of the following:
di(2-hydroxyethyl) ethyl octadecenyl ammonium etho-sulphate cetyltrimethyl ammonium sulphonate cetyltrimethyl ammonium nonylphenyl sulphide dimethyl dodecyl ethyl ammonium etho-sulphate dimethyl ethyl (3-stearyl amino propyl) ammonium etho-sulphate dimethyl ethyl (3-lauryl amino propyl) ammonium etho-sulphate dicocodimethyl ammonium formate dicocodimethyl ammonium borate dicocodimethyl ammonium nonyl phenyl sulphide dicocodimethyl ammonium oxalate.
di(2-hydroxyethyl) ethyl octadecenyl ammonium etho-sulphate cetyltrimethyl ammonium sulphonate cetyltrimethyl ammonium nonylphenyl sulphide dimethyl dodecyl ethyl ammonium etho-sulphate dimethyl ethyl (3-stearyl amino propyl) ammonium etho-sulphate dimethyl ethyl (3-lauryl amino propyl) ammonium etho-sulphate dicocodimethyl ammonium formate dicocodimethyl ammonium borate dicocodimethyl ammonium nonyl phenyl sulphide dicocodimethyl ammonium oxalate.
11. The use according to any one of claims 1 to 10 wherein the use is an indirect injection diesel engine for inhibiting injector nozzle coking.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB87-12442 | 1987-05-27 | ||
| GB878712442A GB8712442D0 (en) | 1987-05-27 | 1987-05-27 | Diesel fuel composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1340601C true CA1340601C (en) | 1999-06-22 |
Family
ID=10617971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000567798A Expired - Fee Related CA1340601C (en) | 1987-05-27 | 1988-05-26 | Diesel fuel compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0293192B1 (en) |
| JP (1) | JP2612926B2 (en) |
| AT (1) | ATE69258T1 (en) |
| AU (1) | AU612153B2 (en) |
| CA (1) | CA1340601C (en) |
| DE (1) | DE3866026D1 (en) |
| ES (1) | ES2026255T3 (en) |
| GB (1) | GB8712442D0 (en) |
| GR (1) | GR3003682T3 (en) |
| WO (1) | WO1988009365A1 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8904785D0 (en) * | 1989-03-02 | 1989-04-12 | Exxon Chemical Patents Inc | Improved fuel oil compositions |
| GB8906027D0 (en) * | 1989-03-16 | 1989-04-26 | Exxon Chemical Patents Inc | Improved fuel oil compositions |
| GB8907801D0 (en) * | 1989-04-06 | 1989-05-17 | Exxon Chemical Patents Inc | Improved fuel oil compositions |
| US5348561A (en) * | 1990-03-01 | 1994-09-20 | Exxon Chemical Patents Inc. | Fuel oil compositions |
| US5207937A (en) * | 1991-04-29 | 1993-05-04 | Mobil Oil Corp. | Amine salts of sulfur-containing alkylated phenols or alkylated naphthols as multifunctional antioxidant and antiwear additives |
| US5641726A (en) * | 1993-06-09 | 1997-06-24 | Lonza, Inc. | Quaternary ammonium carboxylate and borate compositions and preparation thereof |
| US5399762A (en) * | 1993-06-09 | 1995-03-21 | Lonza, Inc. | Quaternary ammonium hydroxide compositions and preparation thereof |
| ZA943999B (en) * | 1993-06-09 | 1995-02-03 | Lonza Ag | Quaternary ammonium and waterproofing/preservative compositions |
| GB9621263D0 (en) | 1996-10-11 | 1996-11-27 | Exxon Chemical Patents Inc | Lubricity additives for fuel oil compositions |
| JP4594626B2 (en) * | 2004-01-30 | 2010-12-08 | 株式会社Ａｄｅｋａ | Lubricating oil composition for internal combustion engine lubricating oil or drive system lubricating oil |
| AU2011211398B2 (en) * | 2005-06-16 | 2014-10-02 | The Lubrizol Corporation | Quaternary ammonium salts for use in fuels and lubricants |
| EP3406692A1 (en) * | 2005-06-16 | 2018-11-28 | The Lubrizol Corporation | Fuel composition comprising a quaternary ammonium salt detergent |
| EP1900795A1 (en) * | 2006-09-07 | 2008-03-19 | Infineum International Limited | Method and use for the prevention of fuel injector deposits |
| US20080113890A1 (en) | 2006-11-09 | 2008-05-15 | The Lubrizol Corporation | Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound |
| US8153570B2 (en) | 2008-06-09 | 2012-04-10 | The Lubrizol Corporation | Quaternary ammonium salt detergents for use in lubricating compositions |
| PL3381998T3 (en) | 2009-05-15 | 2023-12-04 | The Lubrizol Corporation | Quaternary ammonium ester salts |
| US20110112328A1 (en) * | 2009-11-06 | 2011-05-12 | Drovetskaya Tatiana V | Difunctional, Amine-Based Surfactants, and Their Precursors, Preparation, Compositions and Use |
| GB201001920D0 (en) * | 2010-02-05 | 2010-03-24 | Innospec Ltd | Fuel compostions |
| GB201003973D0 (en) | 2010-03-10 | 2010-04-21 | Innospec Ltd | Fuel compositions |
| US20120010112A1 (en) | 2010-07-06 | 2012-01-12 | Basf Se | Acid-free quaternized nitrogen compounds and use thereof as additives in fuels and lubricants |
| US9574149B2 (en) * | 2011-11-11 | 2017-02-21 | Afton Chemical Corporation | Fuel additive for improved performance of direct fuel injected engines |
| EP2604674A1 (en) * | 2011-12-12 | 2013-06-19 | Basf Se | Use of quaternised alkylamine as additive in fuels and lubricants |
| US8690970B2 (en) | 2012-02-24 | 2014-04-08 | Afton Chemical Corporation | Fuel additive for improved performance in fuel injected engines |
| US8894726B2 (en) | 2012-06-13 | 2014-11-25 | Afton Chemical Corporation | Fuel additive for improved performance in fuel injected engines |
| CN102898317B (en) * | 2012-10-12 | 2015-04-22 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| EP2912148A1 (en) * | 2012-10-23 | 2015-09-02 | The Lubrizol Corporation | Diesel detergent without a low molecular weight penalty |
| US9458400B2 (en) | 2012-11-02 | 2016-10-04 | Afton Chemical Corporation | Fuel additive for improved performance in direct fuel injected engines |
| US9017431B2 (en) | 2013-01-16 | 2015-04-28 | Afton Chemical Corporation | Gasoline fuel composition for improved performance in fuel injected engines |
| PL3653689T3 (en) | 2013-06-07 | 2023-08-07 | Basf Se | Use with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid of quaternised nitrogen compounds as additives in fuels and lubricants |
| CN103570561A (en) * | 2013-09-27 | 2014-02-12 | 江南大学 | Synthesis of tetrameric quaternary ammonium salt |
| US8974551B1 (en) | 2014-02-19 | 2015-03-10 | Afton Chemical Corporation | Fuel additive for improved performance in fuel injected engines |
| US9677020B2 (en) | 2014-06-25 | 2017-06-13 | Afton Chemical Corporation | Hydrocarbyl soluble quaternary ammonium carboxylates and fuel compositions containing them |
| GB201413355D0 (en) | 2014-07-28 | 2014-09-10 | Innospec Ltd | Compositons and methods |
| US9340742B1 (en) | 2015-05-05 | 2016-05-17 | Afton Chemical Corporation | Fuel additive for improved injector performance |
| US11390821B2 (en) | 2019-01-31 | 2022-07-19 | Afton Chemical Corporation | Fuel additive mixture providing rapid injector clean-up in high pressure gasoline engines |
| US11873461B1 (en) | 2022-09-22 | 2024-01-16 | Afton Chemical Corporation | Extreme pressure additives with improved copper corrosion |
| US11795412B1 (en) | 2023-03-03 | 2023-10-24 | Afton Chemical Corporation | Lubricating composition for industrial gear fluids |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB716187A (en) * | 1951-06-04 | 1954-09-29 | Lubrizol Corp | Substituted diphenyl ether sulphonate sulphides |
| US3158647A (en) * | 1955-10-05 | 1964-11-24 | Gulf Research Development Co | Quaternary ammonium fatty, phenate and naphthenate salts |
| US3033665A (en) * | 1958-08-01 | 1962-05-08 | Gulf Research Development Co | Nonstalling gasoline motor fuel |
| US3169983A (en) * | 1962-06-11 | 1965-02-16 | United States Borax Chem | Quaternary ammonium glycol monoborate salts |
| GB984496A (en) | 1962-10-03 | 1965-02-24 | Fernseh Gmbh | Circuit arrangement for stabilizing the beam current of an image-orthicon pickup tube |
| US3361793A (en) * | 1964-02-10 | 1968-01-02 | Millmaster Onyx Corp | Microbiologically active quaternary ammonium compounds |
| US3362801A (en) * | 1965-08-02 | 1968-01-09 | Gulf Research Development Co | Hydrocarbon oil stabilization |
| US3493354A (en) * | 1967-02-27 | 1970-02-03 | Monsanto Chemicals | Diesel fuel additive |
| US3560507A (en) * | 1968-02-27 | 1971-02-02 | Millmaster Onyx Corp | Quaternary ammonium alkenyl succinates |
| EP0151621B1 (en) * | 1983-07-29 | 1990-05-02 | Chevron Research And Technology Company | Quaternary deposit control additives |
| US4626259A (en) * | 1985-10-31 | 1986-12-02 | Ethyl Corporation | Fuel compositions |
-
1987
- 1987-05-27 GB GB878712442A patent/GB8712442D0/en active Pending
-
1988
- 1988-05-25 WO PCT/GB1988/000415 patent/WO1988009365A1/en unknown
- 1988-05-25 JP JP63504490A patent/JP2612926B2/en not_active Expired - Lifetime
- 1988-05-25 AT AT88304753T patent/ATE69258T1/en not_active IP Right Cessation
- 1988-05-25 EP EP88304753A patent/EP0293192B1/en not_active Expired - Lifetime
- 1988-05-25 DE DE8888304753T patent/DE3866026D1/en not_active Expired - Lifetime
- 1988-05-25 ES ES198888304753T patent/ES2026255T3/en not_active Expired - Lifetime
- 1988-05-25 AU AU17945/88A patent/AU612153B2/en not_active Ceased
- 1988-05-26 CA CA000567798A patent/CA1340601C/en not_active Expired - Fee Related
-
1992
- 1992-01-30 GR GR920400108T patent/GR3003682T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR3003682T3 (en) | 1993-03-16 |
| WO1988009365A1 (en) | 1988-12-01 |
| DE3866026D1 (en) | 1991-12-12 |
| ES2026255T3 (en) | 1992-04-16 |
| AU612153B2 (en) | 1991-07-04 |
| JPH01503393A (en) | 1989-11-16 |
| ATE69258T1 (en) | 1991-11-15 |
| EP0293192B1 (en) | 1991-11-06 |
| EP0293192A1 (en) | 1988-11-30 |
| JP2612926B2 (en) | 1997-05-21 |
| GB8712442D0 (en) | 1987-07-01 |
| AU1794588A (en) | 1988-12-21 |
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