CA2005707A1 - Fuel stabilizer composition - Google Patents
Fuel stabilizer compositionInfo
- Publication number
- CA2005707A1 CA2005707A1 CA002005707A CA2005707A CA2005707A1 CA 2005707 A1 CA2005707 A1 CA 2005707A1 CA 002005707 A CA002005707 A CA 002005707A CA 2005707 A CA2005707 A CA 2005707A CA 2005707 A1 CA2005707 A1 CA 2005707A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- fuel
- hydrocarbyl
- middle distillate
- substituent
- 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.)
- Abandoned
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
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
The present invention deals with minimizing color formation in middle distillate fuel oils by treating the fuel oil with an aromatic hydroxyl containing compound which is hydrocarbyl substituted, and reacted with a polyamine and an aldehyde or ketone.
The present invention deals with minimizing color formation in middle distillate fuel oils by treating the fuel oil with an aromatic hydroxyl containing compound which is hydrocarbyl substituted, and reacted with a polyamine and an aldehyde or ketone.
Description
~1057(~
FUEL STABILIZER COMPOSITION
BACKGROUND OF THE INVENTION
Field of the invention.
This invention relates to stabilizing fuels, in particular diesel fuels, against discoloration which is sometimes associated with formation of insoluble material.
INTRODUCTION TO THE INVENTION
Fuels generally, and in particular middle distillate fuels are susceptible to the formation of insoluble materials. The insolubles cause blockages in fuel lines, fuel filters and in exaggerated situations in storage tanks. The fuel insoluble materials may also manifest as blockage of a fuel injector tip in a diesel engine.
Wherever the location of the gelation, the fuel will not flow and thus the intended usage of the fuel is not possible.
The formation of insolubles in a middle distillate fuel is usually associated with a color change in the fuel. All color changes in a middle distillate fuel do not, however, indicate that insolubles formation is immi-nent. Accordingly, when discoloration of the middle distillate fuel is observed, the user will not know if it is safe to utilize the fuel. As testing of small quanti-ties of fuel for tendencies to form insolubles is imprac-tical the consumer must rapidly consume the fuel. Even rapid consumption of the fuel is no guarantee that the fuel will not have insolubles form before the fuel is exhausted. Alternatively, the fuel may be returned to the distributor or treated to prevent insolubles formation either of which is a major expense.
Z~0~707 Accordingly, the present invention deals with inhibiting color formation in fuels in which the discoloration may or may not be related to insolubles formation. The compositions herein also are useful in treating middle distillate fuels to prevent insolubles formation.
It is known from United States Patent 3,351,662 issued November 7, 1967 to Chamot that normally liquid petroleum distillate fractions may be treated for color and sludge through the use of organic polyamines with at least one primary amino group reacted with formaldehyde or acetaldehyde and hydroxybenzaldehyde. Chamot makes similar disclosures in United States Patent 3,184,294 issued May 18, 1965. Newkirk in United States Patent 3,654,158 issued April 4, 1972 discloses inhibiting corrosion in hydrocarbon systems through the use of bis-1,3-alkylamino-2 propanol.
United States Patent 4,647,290 issued March 3, 1987 to Reid describes color stabilized distillate fuels containing N-(2-aminoethyl)piperazine and N,N-diethyl-hydroxylamine. Reid makes similar disclosures in United States Patent 4,648,885 issued March 10, 1987 and further includes in his color stabilizing system triethylenetetra-amine. Lastly, Reid describes similar chemistry in United States Patent 4,647,289 also issued March 3, 1987.
United States Patent 3,936,279 issued February 3, 1976 to Alink describes the use of hexahydropyrimidines to inhibit distillate fuel deterioration. Thompson et al in United States Patent 4,311,841 issued January 19, 1982 describes the further use of hexahydropyrimidines as deterioration inhibitors in hydrocarbon fuel. Gattuso in United States Patent 4,003,718 issued January 18, 1977 describes the use of substituted tetrahydropyrimidines as being useful in petroleum distillates such as gasoline.
Kwong et al in Unites States Patent 4,284,415 issued August 18, 1981 describes inhibiting sedimentation and retarding degradation of hydrocarbon fuels through the use 2~0~7~7 of a reaction product of an alkoxyalkylamine with an epihalohydrin. Kwong discloses similar chemistry relating to poly(oxyalkylene)amine reaction products with an epihalohydrin for inhibiting sedimentation and retarding degradation of hydrocarbon fuels in United States Patent 4,239,497 issued December 16, 1980. Hanson in United States Patent 4,242,212 issued December 30, 1980 describes Mannich additives formed from a 2,4- or 2,6-ditertiary alkyl "hindered" phenol, a polyamine, a formaldehyde yielding reagent and at least one hydrocarbon compound with at least one active or acidic hydrogen. United States Patent 3,948,619 to Worrel issued April 6, 1976 describes cleaning of an internal combustion enqine using gasoline containing a detergent amount of the condensation product of phenol and preferably a high molecular weight alkylphenol, an aldehyde and an amine having a free -N(H)-group. It is disclosed in United States Patent 4,509,932 issued April 9, 1985 to Braxton that a minor amount of an alkyldiethylamine may be added to distillate fuel to stabilize against deterioration.
Otto in United States Patent 3,649,229 issued March 14, 1972 describes the reaction products of high molecular weight alkyl substituted hydroxy aromatic compounds, amines and aldehydes as being a detergency improver for a liquid hydrocarbon fuel.
Hanlon in United States Patent 4,553,979 issued No-vember 19, 1985 discloses reducing coking around injector nozzles in distillate fuel compositions containing an organic nitrate ignition accelerator and the condensation product of a phenol, preferably a high molecular weight alkylphenol, an aldehyde and an amine having a -N(H)-group. Sung et al in United States Patent 4,501,595 issued February 26, 1985 discloses a diesel oil of im-proved storage stability containing the condensate of tetraethylenepentamine, paraformaldehyde 2,6-di-t-butyl-phenol and polyisobutenyl succinic anhydride. United States Patent 4,166,726 issued September 4, 1979 to Harle ~05707 describes a fuel additive and fuel composition wherein the additive comprises a polyalkylene amine and the reaction product of an alkylphenol, an aldehyde and an amine. Jackisch in United States Patent 4,116,644 issued September 26, 1978 describes cleaning fuel induction systems through the use of gasoline containing a phenol, and the condensation product of an alkylphenol, an alde-hyde and an amine having an -N(H)- group. Chibnik in United States Patent 4,083,699 issued April 11, 1978 des-cribes the detergency properties of a fuel or lubricant being improved by adding a Mannich base product prepared by reacting a high molecular weight alkyl substituted hydroxyaromatic compound, a polyoxyethylene polyamine and an aldehyde.
Unites States Patent 3,944,397 issued March 16, 1976 to Gardiner et al describes the preparation of a gasoline composition and a benzyl polyamine compound where the benzyl group is hydroxy-substituted. Gardiner also des-cribes concentrates of the active ingredient in a hydro-carbon solvent. Japanese Laid-Open patent publication no.
63-386 filed June 19, 1986 describes fuel oil stabilizer compositions. Japanese 63 30,594 describes light cycle oils from desulfurized heavy oils which are hue stabli-lized with a compound containing phenolic and polyamine structures.
While many compositions have been utilized in the art for middle distillate fuel stabilization and color protec-tion none have proved to be as useful as the compositions of the present invention. Accordingly this invention relates to a method of inhibiting color formation and avoiding insolubles formation in middle distillate fuel compositions.
To the extent that the references cited herein are applicable to the present invention thev are herein in-corporated by reference. Throughout the specification andclaims, percentages and ratios are by weight, and tempera-tures are in degrees Celsius unless otherwise indicated.
: : .
20~357~7 Ranges are exemplary and may be combined. Pressures where given are in KPa gauge unless otherwise indicated.
2~0~7(~7 SUMMARY OF THE INVENTION
The present invention deals with a composition comprising:
(A) a middle distillate fuel; and (B) the reaction product of a hydrocarbyl and hy-droxy substituted aromatic compound; an aldehyde or ketone; and at least one alkylene polyamine.
This invention further describes a composition comprising:
(A) a middle distillate fuel; and, (B) the reaction product of a monohydrocarbyl sub-stituted phenol; formaldehyde; and ethylene diamine.
Yet another feature of the present invention is a composition which comprises:
(A) A middle distillate fuel; and, (B) a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R;
wherein R is at least one hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxyl containing moiety.
A further feature of the invention is a composition comprising:
(A) a middle distillate fuel; and, (B) the reaction product of [R]mPh(OH)[C(Rl)(R2)X] ;
and an alkylene polyamine, wherein Ph(OH) is a phenolic residue, R is at least one hydrocarbyl substituent; Rl is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; m is 0 to 2 wherein n+m is not greater than 5.
This invention also describes a method of inhibiting color formation in (A) middle distillate fuel by adding to the fuel a sufficient amount of (B) the reaction product of a hydrocarbyl and hydroxy substituted aromatic com-pound; an aldehyde or ketone; and an alkylene polyamine.
The present invention also describes a method forinhibiting color formation in a middle distillate fuel 2~707 comprising contacting the middle distillate fuel (A) with a sufficient amount of a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R wherein R is a hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxy moiety.
Still another feature of the present invention is a method for inhibiting color formation in a middle distil-late fuel comprising contacting the middle distillate fuel (A) with (B) the reaction product of [R]mPh(OH)[C(Rl)(R2)X]n; and an alkylene polyamine, wherein Ph(OH) is a phenolic residue; R is at least one hydrocarbyl substituent; Rl is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; and m is 0 to 2 wherein n+m is not greater than 5 wherein the amount of (B) is sufficient to inhibit color formation in (A).
2~30~7~7 DETAILED DESCRIPTION OF THE INVENTION
The present invention as previously described deals with inhibiting or minimizing color formation in a middle distillate fuel. Typically a middle distillate fuel is a hydrocarbon source fuel which is used in a power plant, in home heating oils, jet fuels, kerosene or as a diesel fuel. In particular the present invention deals with diesel fuels.
Diesel fuels are typically defined by a specification prescribed by the American Society for Testing Materials.
This specification known as ASTM D 975-81 adequately describes the major aspects of the present invention including the definition of a diesel fuel.
As previously noted, there need be nothing wrong with the diesel fuel in order to treat the fuel with the compo-sitions of the present invention. That is, it is not known exactly why some diesel fuels change color and form insolubles while other fuels may change color and do not form insolubles. One theory is that high sulfur content diesel fuels are more susceptible to forming insolubles and discoloration, particularly when exposed to heat, than are diesel fuels which are essentially free of sul-fur. Sulfur is usually present in fuels from naturally occurring organosulfur compounds. Sulfur in a middle distillate fuel may be present as an unintended by-product of refining such that the sulfur is reacted into one or more organic components in the middle distillate fuel.
Typically, when sulfur is found to be a problem in a mid-dle distillate fuel it is because the sulfur is present at 0.1 ppm to 20,000 ppm as sulfur based on the weight of the middle distillate fuel.
In any event, as the ultimate customer has no way of knowing if the fuel will form insolubles due to an onset of color change, the present invention gives the assurance of obtaining a product in which color formation is minimized.
J7~)7 g The next aspect of the present invention is the discussion of the hydrocarbyl and hydroxy substituted aromatic compound. The hydrocarbyl and hydroxy substi-tuted aromatic compound may be a mononuclear or polynucle-ar aromatic compound. It is preferred that mononucleararomatic compounds are the basis for the hydrocarbyl and hydroxy substituted aromatic compound. The hydroxy groups are typically present as a monohydroxy group on the mono-nuclear aromatic compound. At least, it is desired that there only be one hydroxy group per aromatic nuclear group. The hydrocarbyl substituent on the hydrocarbyl and hydroxy substituted aromatic compound typically contains up to 150 carbon atoms, preferably from 2 to about 30 carbon atoms, more preferably about 3 to about 20 carbon atoms, and most preferably about 6 to about 18 carbon atoms.
The hydrocarbyl substituent may be saturated or un-saturated although the former is preferable. Branched chain hydrocarbyl substituents are preferred to straight chain hydrocarbyl substituents. Polyisopropylene and polyisobutylene are the preferred hydrocarbyl substituents.
In one aspect of the invention the hydrocarbyl sub-stituted aromatic hydroxyl containing moiety as shown in the Summary has R as previously described with m being from 0 to 2, preferably 1. The values of Rl and R2 are independently hydrogen or a hydrocarbyl group. Where Rl and R2 are other than the preferred hydrogens, the hydro-carbyl groups typically contain from 1 to 5 carbon atoms.
Thus Rl or R2 may conveniently be methyl or ethyl groups.
The value of X is defined as (R3)2N-, a hydroxyl (-OH), or OR3 where R3 is a hydrocarbyl group as described for R.
The value of n is from 1 to 3 and is preferably 1. The sum of n plus m is not greater than 5, e.g. the remaining valences on a mononuclear aromatic phenol.
The second component of the reaction product (B) is an aldehyde or a ketone. The aldehydes are of the formula 2~0~707 R4(C=O)H whereas the ketone is of the formula R5(C=O3R6.
R4 is hydrogen or a hydrocarbyl group in an aldehyde. The values of R5 and R6 are such that each are hydrocarbyl groups in a ketone. The foregoing hydrocarbyl groups typ-ically contain from 0 to 10 carbon atoms and are prefer-ably saturated groups.
Typical examples of the aldehyde or ketone include formaldehyde, acetaldehyde, propanal, dimethyl ketone, diethyl ketone, methylisobutyl ketone, and the like. Pre-ferably the aldehyde is formaldehyde and may be used inany form such as formalin or paraformaldehyde.
The alkylene polyamine utilized in the present inven-tion is typically of the formula H2N(CnH2nNH)X(caH2aNH)bccH2c 2 wherein n is an integer, a is an integer, b is an integer, and c is an integer. Typically the values for the compo-nents are where x, a, and b are all zero and c is 2. The preferred polyamine monomeric units are based on ethylene diamine or propylene diamine. The preferred species in the present invention is ethylene diamine, or its polymers triethylene tetramine, tetraethylene pentamine or penta-ethylene hexamine.
An example of the preparation of the reaction product (B) is shown below as Example I-A.
EXAMPLE I-A
Polypropylenephenol (polypropylene M.W. 168) contain-ing 74~ para-polypropylene substituent, 5,300 grams, tet-raethylenepentamine 1,912 grams, and toluene 1,775 grams are placed in a reactor, and 1,686 grams of 36~ aqueous formaldehyde are added over a period of 90 minutes. The reaction mixture is refluxed for 11 hours, during which period 1,440 ml of water is separated. The reaction mixture is filtered through diatomaceous earth.
The neat recovered product will have 4.5~ by weight nitrogen content. Theoretical is 4.6% nitrogen.
Some of the alkyl- and hydroxy-substituted benzyl polyamine containing different amounts of benzyl groups 7~)7 prepared by using a procedure essentially as described above are listed below. In each case the desired product is obtained by choosing the proper molar ratios of poly-propylenephenol, formaldehyde and polyamine. The poly-propylenephenol (polypropylene M.W. 168) contains about60~ of the polvpropylene group in the para position.
Mole Ratio of Polypropylenephenol:HCHO:Polyamine Polyamine Preparation B 2:2:1 ethylenediamine 10 Preparation C 1:1:1 triethylenetetramine Preparation D 2:2:1 triethylenetetramine Preparation E 3:3:1 triethylenetetramine Preparation F 4:4:1 triethylenetetramine Preparation G 1:1:1 tetraethylenepentamine 15 Preparation H 2:2:1 tetraethylenepentamine Preparation I 3:3:1 tetraethylenepentamine Preparation J 5:5:1 tetraethylenepentamine Preparation K 5:10:1 triethylenetetramine Generally, the molar ratio of the aromatic compound, the aldehyde and the alkylene polyamine is respectively about 1:1:1 to about 5:10:1, preferably 2:1:1 to 3:3:1, and is most preferably 2:2:1. For instance, respective molar ratios of the hydrocarbyl and hydroxy substituted aromatic compound; the aldehyde or ketone; and the alkyl-ene polyamine are 2:2:1; 1:1:1; 2:1:2; 1:2:2; and the like.
The general reaction conditions are to premix the alkylene polyamine with the hydrocarbyl and hydroxy substituted aromatic compound together with any suitable solvent. Suitable solvents include xylene, toluene or benzene. The aldehyde or ketone may be simply added as a convenient aqueous mixture thereof.
The reaction proceeds at reflux for a sufficient period of time to ensure substantial completion of the desired reaction. Typically, the reaction times vary from one hour to twenty-four hours. If desired, the aldehyde or ketone may be added intermittently. A preferred method ~0~7~)'7 for conducting the reaction is to remove water as it is formed together with any incidental water which is present from the reactants.
The product may be recovered in the solvent for convenience and filtered through suitable filtering material.
;~0 ~7~)7 USAGE OF THE PRODUCT
The products of the present invention are typically utilized as a very small quantity based on the total middle distillate fuel treated. The amount of tB~ em-ployed is simply that sufficient to stabilize a given fuelagainst color deterioration. Typically the amount of the reaction product (B) will be about 5 parts to about 2000 parts per million parts of fuel treated. A preferred range for the utilization of the reaction product (B) in fuel is from 50 parts to 1,500 parts per million parts of fuel.
The reaction product (B) is conveniently blended directly into the fuel at the refinery. As component (B) tends to be fuel soluble very little mixing is required and it may be metered directly into a fuel stream. If desired the reaction product (B) may be premixed with a quantity of suitable solvent (including the middle distil-late fuel or component thereof) and then diluted out in the fuel to be treated. The solvents are conveniently those used to prepare (B).
The following is an example of the treatment of a diesel fuel according to the present invention.
X~O ~ 7 EXA.~PLE
A diesel fuel is obtained and combined with the active of Example I-A. To facilitate mixing the active is first diluted with xylene at a 4:1 active to solvent weight ratio. The active is added to the fuel at 115 parts per million parts of the fuel.
The product is then tested for storage stability. At the end of the test period the color and insolubles formation is determined. The product described herein achieved a pass rating for color and insolubles formation.
Substantially similar results are obtained using the active at 165 ppm, 330 ppm, 495 ppm, 742.5 ppm and 1000 ppm. Larger amounts of the active provide longer protec-tion for the fuel. Further use of Preparations B-K give similar results.
FUEL STABILIZER COMPOSITION
BACKGROUND OF THE INVENTION
Field of the invention.
This invention relates to stabilizing fuels, in particular diesel fuels, against discoloration which is sometimes associated with formation of insoluble material.
INTRODUCTION TO THE INVENTION
Fuels generally, and in particular middle distillate fuels are susceptible to the formation of insoluble materials. The insolubles cause blockages in fuel lines, fuel filters and in exaggerated situations in storage tanks. The fuel insoluble materials may also manifest as blockage of a fuel injector tip in a diesel engine.
Wherever the location of the gelation, the fuel will not flow and thus the intended usage of the fuel is not possible.
The formation of insolubles in a middle distillate fuel is usually associated with a color change in the fuel. All color changes in a middle distillate fuel do not, however, indicate that insolubles formation is immi-nent. Accordingly, when discoloration of the middle distillate fuel is observed, the user will not know if it is safe to utilize the fuel. As testing of small quanti-ties of fuel for tendencies to form insolubles is imprac-tical the consumer must rapidly consume the fuel. Even rapid consumption of the fuel is no guarantee that the fuel will not have insolubles form before the fuel is exhausted. Alternatively, the fuel may be returned to the distributor or treated to prevent insolubles formation either of which is a major expense.
Z~0~707 Accordingly, the present invention deals with inhibiting color formation in fuels in which the discoloration may or may not be related to insolubles formation. The compositions herein also are useful in treating middle distillate fuels to prevent insolubles formation.
It is known from United States Patent 3,351,662 issued November 7, 1967 to Chamot that normally liquid petroleum distillate fractions may be treated for color and sludge through the use of organic polyamines with at least one primary amino group reacted with formaldehyde or acetaldehyde and hydroxybenzaldehyde. Chamot makes similar disclosures in United States Patent 3,184,294 issued May 18, 1965. Newkirk in United States Patent 3,654,158 issued April 4, 1972 discloses inhibiting corrosion in hydrocarbon systems through the use of bis-1,3-alkylamino-2 propanol.
United States Patent 4,647,290 issued March 3, 1987 to Reid describes color stabilized distillate fuels containing N-(2-aminoethyl)piperazine and N,N-diethyl-hydroxylamine. Reid makes similar disclosures in United States Patent 4,648,885 issued March 10, 1987 and further includes in his color stabilizing system triethylenetetra-amine. Lastly, Reid describes similar chemistry in United States Patent 4,647,289 also issued March 3, 1987.
United States Patent 3,936,279 issued February 3, 1976 to Alink describes the use of hexahydropyrimidines to inhibit distillate fuel deterioration. Thompson et al in United States Patent 4,311,841 issued January 19, 1982 describes the further use of hexahydropyrimidines as deterioration inhibitors in hydrocarbon fuel. Gattuso in United States Patent 4,003,718 issued January 18, 1977 describes the use of substituted tetrahydropyrimidines as being useful in petroleum distillates such as gasoline.
Kwong et al in Unites States Patent 4,284,415 issued August 18, 1981 describes inhibiting sedimentation and retarding degradation of hydrocarbon fuels through the use 2~0~7~7 of a reaction product of an alkoxyalkylamine with an epihalohydrin. Kwong discloses similar chemistry relating to poly(oxyalkylene)amine reaction products with an epihalohydrin for inhibiting sedimentation and retarding degradation of hydrocarbon fuels in United States Patent 4,239,497 issued December 16, 1980. Hanson in United States Patent 4,242,212 issued December 30, 1980 describes Mannich additives formed from a 2,4- or 2,6-ditertiary alkyl "hindered" phenol, a polyamine, a formaldehyde yielding reagent and at least one hydrocarbon compound with at least one active or acidic hydrogen. United States Patent 3,948,619 to Worrel issued April 6, 1976 describes cleaning of an internal combustion enqine using gasoline containing a detergent amount of the condensation product of phenol and preferably a high molecular weight alkylphenol, an aldehyde and an amine having a free -N(H)-group. It is disclosed in United States Patent 4,509,932 issued April 9, 1985 to Braxton that a minor amount of an alkyldiethylamine may be added to distillate fuel to stabilize against deterioration.
Otto in United States Patent 3,649,229 issued March 14, 1972 describes the reaction products of high molecular weight alkyl substituted hydroxy aromatic compounds, amines and aldehydes as being a detergency improver for a liquid hydrocarbon fuel.
Hanlon in United States Patent 4,553,979 issued No-vember 19, 1985 discloses reducing coking around injector nozzles in distillate fuel compositions containing an organic nitrate ignition accelerator and the condensation product of a phenol, preferably a high molecular weight alkylphenol, an aldehyde and an amine having a -N(H)-group. Sung et al in United States Patent 4,501,595 issued February 26, 1985 discloses a diesel oil of im-proved storage stability containing the condensate of tetraethylenepentamine, paraformaldehyde 2,6-di-t-butyl-phenol and polyisobutenyl succinic anhydride. United States Patent 4,166,726 issued September 4, 1979 to Harle ~05707 describes a fuel additive and fuel composition wherein the additive comprises a polyalkylene amine and the reaction product of an alkylphenol, an aldehyde and an amine. Jackisch in United States Patent 4,116,644 issued September 26, 1978 describes cleaning fuel induction systems through the use of gasoline containing a phenol, and the condensation product of an alkylphenol, an alde-hyde and an amine having an -N(H)- group. Chibnik in United States Patent 4,083,699 issued April 11, 1978 des-cribes the detergency properties of a fuel or lubricant being improved by adding a Mannich base product prepared by reacting a high molecular weight alkyl substituted hydroxyaromatic compound, a polyoxyethylene polyamine and an aldehyde.
Unites States Patent 3,944,397 issued March 16, 1976 to Gardiner et al describes the preparation of a gasoline composition and a benzyl polyamine compound where the benzyl group is hydroxy-substituted. Gardiner also des-cribes concentrates of the active ingredient in a hydro-carbon solvent. Japanese Laid-Open patent publication no.
63-386 filed June 19, 1986 describes fuel oil stabilizer compositions. Japanese 63 30,594 describes light cycle oils from desulfurized heavy oils which are hue stabli-lized with a compound containing phenolic and polyamine structures.
While many compositions have been utilized in the art for middle distillate fuel stabilization and color protec-tion none have proved to be as useful as the compositions of the present invention. Accordingly this invention relates to a method of inhibiting color formation and avoiding insolubles formation in middle distillate fuel compositions.
To the extent that the references cited herein are applicable to the present invention thev are herein in-corporated by reference. Throughout the specification andclaims, percentages and ratios are by weight, and tempera-tures are in degrees Celsius unless otherwise indicated.
: : .
20~357~7 Ranges are exemplary and may be combined. Pressures where given are in KPa gauge unless otherwise indicated.
2~0~7(~7 SUMMARY OF THE INVENTION
The present invention deals with a composition comprising:
(A) a middle distillate fuel; and (B) the reaction product of a hydrocarbyl and hy-droxy substituted aromatic compound; an aldehyde or ketone; and at least one alkylene polyamine.
This invention further describes a composition comprising:
(A) a middle distillate fuel; and, (B) the reaction product of a monohydrocarbyl sub-stituted phenol; formaldehyde; and ethylene diamine.
Yet another feature of the present invention is a composition which comprises:
(A) A middle distillate fuel; and, (B) a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R;
wherein R is at least one hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxyl containing moiety.
A further feature of the invention is a composition comprising:
(A) a middle distillate fuel; and, (B) the reaction product of [R]mPh(OH)[C(Rl)(R2)X] ;
and an alkylene polyamine, wherein Ph(OH) is a phenolic residue, R is at least one hydrocarbyl substituent; Rl is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; m is 0 to 2 wherein n+m is not greater than 5.
This invention also describes a method of inhibiting color formation in (A) middle distillate fuel by adding to the fuel a sufficient amount of (B) the reaction product of a hydrocarbyl and hydroxy substituted aromatic com-pound; an aldehyde or ketone; and an alkylene polyamine.
The present invention also describes a method forinhibiting color formation in a middle distillate fuel 2~707 comprising contacting the middle distillate fuel (A) with a sufficient amount of a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R wherein R is a hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxy moiety.
Still another feature of the present invention is a method for inhibiting color formation in a middle distil-late fuel comprising contacting the middle distillate fuel (A) with (B) the reaction product of [R]mPh(OH)[C(Rl)(R2)X]n; and an alkylene polyamine, wherein Ph(OH) is a phenolic residue; R is at least one hydrocarbyl substituent; Rl is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; and m is 0 to 2 wherein n+m is not greater than 5 wherein the amount of (B) is sufficient to inhibit color formation in (A).
2~30~7~7 DETAILED DESCRIPTION OF THE INVENTION
The present invention as previously described deals with inhibiting or minimizing color formation in a middle distillate fuel. Typically a middle distillate fuel is a hydrocarbon source fuel which is used in a power plant, in home heating oils, jet fuels, kerosene or as a diesel fuel. In particular the present invention deals with diesel fuels.
Diesel fuels are typically defined by a specification prescribed by the American Society for Testing Materials.
This specification known as ASTM D 975-81 adequately describes the major aspects of the present invention including the definition of a diesel fuel.
As previously noted, there need be nothing wrong with the diesel fuel in order to treat the fuel with the compo-sitions of the present invention. That is, it is not known exactly why some diesel fuels change color and form insolubles while other fuels may change color and do not form insolubles. One theory is that high sulfur content diesel fuels are more susceptible to forming insolubles and discoloration, particularly when exposed to heat, than are diesel fuels which are essentially free of sul-fur. Sulfur is usually present in fuels from naturally occurring organosulfur compounds. Sulfur in a middle distillate fuel may be present as an unintended by-product of refining such that the sulfur is reacted into one or more organic components in the middle distillate fuel.
Typically, when sulfur is found to be a problem in a mid-dle distillate fuel it is because the sulfur is present at 0.1 ppm to 20,000 ppm as sulfur based on the weight of the middle distillate fuel.
In any event, as the ultimate customer has no way of knowing if the fuel will form insolubles due to an onset of color change, the present invention gives the assurance of obtaining a product in which color formation is minimized.
J7~)7 g The next aspect of the present invention is the discussion of the hydrocarbyl and hydroxy substituted aromatic compound. The hydrocarbyl and hydroxy substi-tuted aromatic compound may be a mononuclear or polynucle-ar aromatic compound. It is preferred that mononucleararomatic compounds are the basis for the hydrocarbyl and hydroxy substituted aromatic compound. The hydroxy groups are typically present as a monohydroxy group on the mono-nuclear aromatic compound. At least, it is desired that there only be one hydroxy group per aromatic nuclear group. The hydrocarbyl substituent on the hydrocarbyl and hydroxy substituted aromatic compound typically contains up to 150 carbon atoms, preferably from 2 to about 30 carbon atoms, more preferably about 3 to about 20 carbon atoms, and most preferably about 6 to about 18 carbon atoms.
The hydrocarbyl substituent may be saturated or un-saturated although the former is preferable. Branched chain hydrocarbyl substituents are preferred to straight chain hydrocarbyl substituents. Polyisopropylene and polyisobutylene are the preferred hydrocarbyl substituents.
In one aspect of the invention the hydrocarbyl sub-stituted aromatic hydroxyl containing moiety as shown in the Summary has R as previously described with m being from 0 to 2, preferably 1. The values of Rl and R2 are independently hydrogen or a hydrocarbyl group. Where Rl and R2 are other than the preferred hydrogens, the hydro-carbyl groups typically contain from 1 to 5 carbon atoms.
Thus Rl or R2 may conveniently be methyl or ethyl groups.
The value of X is defined as (R3)2N-, a hydroxyl (-OH), or OR3 where R3 is a hydrocarbyl group as described for R.
The value of n is from 1 to 3 and is preferably 1. The sum of n plus m is not greater than 5, e.g. the remaining valences on a mononuclear aromatic phenol.
The second component of the reaction product (B) is an aldehyde or a ketone. The aldehydes are of the formula 2~0~707 R4(C=O)H whereas the ketone is of the formula R5(C=O3R6.
R4 is hydrogen or a hydrocarbyl group in an aldehyde. The values of R5 and R6 are such that each are hydrocarbyl groups in a ketone. The foregoing hydrocarbyl groups typ-ically contain from 0 to 10 carbon atoms and are prefer-ably saturated groups.
Typical examples of the aldehyde or ketone include formaldehyde, acetaldehyde, propanal, dimethyl ketone, diethyl ketone, methylisobutyl ketone, and the like. Pre-ferably the aldehyde is formaldehyde and may be used inany form such as formalin or paraformaldehyde.
The alkylene polyamine utilized in the present inven-tion is typically of the formula H2N(CnH2nNH)X(caH2aNH)bccH2c 2 wherein n is an integer, a is an integer, b is an integer, and c is an integer. Typically the values for the compo-nents are where x, a, and b are all zero and c is 2. The preferred polyamine monomeric units are based on ethylene diamine or propylene diamine. The preferred species in the present invention is ethylene diamine, or its polymers triethylene tetramine, tetraethylene pentamine or penta-ethylene hexamine.
An example of the preparation of the reaction product (B) is shown below as Example I-A.
EXAMPLE I-A
Polypropylenephenol (polypropylene M.W. 168) contain-ing 74~ para-polypropylene substituent, 5,300 grams, tet-raethylenepentamine 1,912 grams, and toluene 1,775 grams are placed in a reactor, and 1,686 grams of 36~ aqueous formaldehyde are added over a period of 90 minutes. The reaction mixture is refluxed for 11 hours, during which period 1,440 ml of water is separated. The reaction mixture is filtered through diatomaceous earth.
The neat recovered product will have 4.5~ by weight nitrogen content. Theoretical is 4.6% nitrogen.
Some of the alkyl- and hydroxy-substituted benzyl polyamine containing different amounts of benzyl groups 7~)7 prepared by using a procedure essentially as described above are listed below. In each case the desired product is obtained by choosing the proper molar ratios of poly-propylenephenol, formaldehyde and polyamine. The poly-propylenephenol (polypropylene M.W. 168) contains about60~ of the polvpropylene group in the para position.
Mole Ratio of Polypropylenephenol:HCHO:Polyamine Polyamine Preparation B 2:2:1 ethylenediamine 10 Preparation C 1:1:1 triethylenetetramine Preparation D 2:2:1 triethylenetetramine Preparation E 3:3:1 triethylenetetramine Preparation F 4:4:1 triethylenetetramine Preparation G 1:1:1 tetraethylenepentamine 15 Preparation H 2:2:1 tetraethylenepentamine Preparation I 3:3:1 tetraethylenepentamine Preparation J 5:5:1 tetraethylenepentamine Preparation K 5:10:1 triethylenetetramine Generally, the molar ratio of the aromatic compound, the aldehyde and the alkylene polyamine is respectively about 1:1:1 to about 5:10:1, preferably 2:1:1 to 3:3:1, and is most preferably 2:2:1. For instance, respective molar ratios of the hydrocarbyl and hydroxy substituted aromatic compound; the aldehyde or ketone; and the alkyl-ene polyamine are 2:2:1; 1:1:1; 2:1:2; 1:2:2; and the like.
The general reaction conditions are to premix the alkylene polyamine with the hydrocarbyl and hydroxy substituted aromatic compound together with any suitable solvent. Suitable solvents include xylene, toluene or benzene. The aldehyde or ketone may be simply added as a convenient aqueous mixture thereof.
The reaction proceeds at reflux for a sufficient period of time to ensure substantial completion of the desired reaction. Typically, the reaction times vary from one hour to twenty-four hours. If desired, the aldehyde or ketone may be added intermittently. A preferred method ~0~7~)'7 for conducting the reaction is to remove water as it is formed together with any incidental water which is present from the reactants.
The product may be recovered in the solvent for convenience and filtered through suitable filtering material.
;~0 ~7~)7 USAGE OF THE PRODUCT
The products of the present invention are typically utilized as a very small quantity based on the total middle distillate fuel treated. The amount of tB~ em-ployed is simply that sufficient to stabilize a given fuelagainst color deterioration. Typically the amount of the reaction product (B) will be about 5 parts to about 2000 parts per million parts of fuel treated. A preferred range for the utilization of the reaction product (B) in fuel is from 50 parts to 1,500 parts per million parts of fuel.
The reaction product (B) is conveniently blended directly into the fuel at the refinery. As component (B) tends to be fuel soluble very little mixing is required and it may be metered directly into a fuel stream. If desired the reaction product (B) may be premixed with a quantity of suitable solvent (including the middle distil-late fuel or component thereof) and then diluted out in the fuel to be treated. The solvents are conveniently those used to prepare (B).
The following is an example of the treatment of a diesel fuel according to the present invention.
X~O ~ 7 EXA.~PLE
A diesel fuel is obtained and combined with the active of Example I-A. To facilitate mixing the active is first diluted with xylene at a 4:1 active to solvent weight ratio. The active is added to the fuel at 115 parts per million parts of the fuel.
The product is then tested for storage stability. At the end of the test period the color and insolubles formation is determined. The product described herein achieved a pass rating for color and insolubles formation.
Substantially similar results are obtained using the active at 165 ppm, 330 ppm, 495 ppm, 742.5 ppm and 1000 ppm. Larger amounts of the active provide longer protec-tion for the fuel. Further use of Preparations B-K give similar results.
Claims (34)
1. A composition comprising:
(A) a middle distillate fuel; and (B) the reaction product of a hydrocarbyl and hydroxy substituted aromatic compound; an aldehyde or ketone; and at least one alkylene polyamine.
(A) a middle distillate fuel; and (B) the reaction product of a hydrocarbyl and hydroxy substituted aromatic compound; an aldehyde or ketone; and at least one alkylene polyamine.
2. The composition of claim 1 wherein the aromatic compound is a monohydroxy aromatic compound.
3. The composition of claim 1 wherein (B) employs an aldehyde.
4. The composition of claim 1 wherein the hydro-carbyl substituent on the aromatic compound is saturated.
5. The composition of claim 1 wherein the alkylene polyamine is ethylene diamine.
6. The composition of claim 4 wherein the hydro-carbyl substituent is a propylene oligomer.
7. The composition of claim 1 wherein the aromatic compound is monohydrocarbyl substituted.
8. The composition of claim 1 wherein the molar ratio of the aromatic compound; the aldehyde; and the alkylene polyamine is respectively about 1:1:1 to 5:10:1.
9. The composition of claim 1 wherein (B) is utilized at about 5 to about 2000 ppm to component (A).
10. The composition of claim 1 wherein the hydro-carbyl substituent of the aromatic compound contains from 2 to about 30 carbon atoms.
11. The composition of claim 3 wherein the aldehyde is formaldehyde.
12. The composition of claim 1 wherein the alkylene polyamine is selected from the group consisting of diethylene triamine and triethylene tetramine.
13. A composition comprising:
(A) a middle distillate fuel; and, (B) the reaction product of a monohydrocarbyl substituted phenol; formaldehyde; and ethylene diamine.
(A) a middle distillate fuel; and, (B) the reaction product of a monohydrocarbyl substituted phenol; formaldehyde; and ethylene diamine.
14. A composition which comprises:
(A) A middle distillate fuel; and, (B) a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R;
wherein R is at least one hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxyl containing moiety.
(A) A middle distillate fuel; and, (B) a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R;
wherein R is at least one hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxyl containing moiety.
15. The composition of claim 14 wherein R is a polypropylene oligomer.
16. The composition of claim 14 wherein R is a single hydrocarbyl substituent on the aromatic group.
17. The composition of claim 14 wherein R is a saturated hydrocarbon.
18. The composition of claim 14 wherein R contains about 6 to about 18 carbon atoms.
19. The composition of claim 14 wherein (B) is present at about 5 to about 2000 ppm based on component (A).
20. A method of inhibiting color formation in (A) a middle distillate fuel by adding to the fuel a sufficient amount of (B) the reaction product of a hydrocarbyl and hydroxy substituted aromatic compound; an aldehyde or ketone; and an alkylene polyamine.
21. The method of claim 20 wherein the fuel is diesel fuel.
22. The method of claim 20 wherein (B) employs formaldehyde.
23. The method of claim 20 wherein (B) is present at 5 ppm to 2000 ppm based on (A).
24. A method for inhibiting color formation in a middle distillate fuel comprising contacting the middle distillate fuel (A) with a sufficient amount of a compound of the formula RPh(OH)CH2NHC2H4NHCH2Ph(OH)R wherein R is a hydrocarbyl substituent, and Ph(OH) is an aromatic hydroxy moiety.
25. The method of claim 24 wherein the fuel is diesel fuel.
26. A composition comprising:
(A) a middle distillate fuel oil; and, (B) the reaction product of [R]mPh(OH)[C(R1)(R2)X]n; and an alkylene polyamine, wherein Ph(OH) is a phenolic residue, R is at least one hydrocarbyl substituent; R1 is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; m is 0 to 2 wherein n+m is not greater than 5.
(A) a middle distillate fuel oil; and, (B) the reaction product of [R]mPh(OH)[C(R1)(R2)X]n; and an alkylene polyamine, wherein Ph(OH) is a phenolic residue, R is at least one hydrocarbyl substituent; R1 is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; m is 0 to 2 wherein n+m is not greater than 5.
27. The composition of claim 26 wherein the alkylene polyamine is ethylene diamine.
28. The composition of claim 26 wherein the hydro-carbyl substituent is a propylene oligomer.
29. The compcsition of claim 26 wherein the weight ratio of (B) is about 5 to about 2000 ppm based on (A).
30. A method for inhibiting color formation in a middle distillate fuel comprising contacting the middle distillate fuel (A) with (B) the reaction product of [R]mPh(OH)[C(R1)(R2)X]n; and an alkylene polyamine, wherein Ph(OH) is a phenolic residue, R is at least one hydrocarbyl substituent; R1 is hydrogen or a hydrocarbyl group; R2 is hydrogen or a hydrocarbyl group; X is (R3)2N-, OH or OR3 where R3 is a hydrocarbyl group; n is from 1 to 3; and m is 0 to 2 wherein n+m is not greater than 5 wherein the amount of (B) is sufficient to inhibit color formation in (A).
31. The method of claim 30 wherein the alkylene polyamine is ethylene diamine.
32. The method of claim 30 wherein the hydrocarbyl substituent R is a propylene oligomer and m is 1.
33. The method of claim 30 wherein the molar ratio of [R]mPh(OH)[C(R1(R2)X]n;
to the polyamine respectively is about 1:1 to about 3:1.
to the polyamine respectively is about 1:1 to about 3:1.
34. The method of claim 30 wherein the weight ratio of B is about 5 to about 2000 ppm based on (A).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28781888A | 1988-12-21 | 1988-12-21 | |
| US07/287,818 | 1988-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2005707A1 true CA2005707A1 (en) | 1990-06-21 |
Family
ID=23104490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002005707A Abandoned CA2005707A1 (en) | 1988-12-21 | 1989-12-15 | Fuel stabilizer composition |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0403624A1 (en) |
| JP (1) | JPH03502819A (en) |
| CN (1) | CN1044118A (en) |
| AU (1) | AU4748890A (en) |
| BR (1) | BR8907269A (en) |
| CA (1) | CA2005707A1 (en) |
| ES (1) | ES2018123A6 (en) |
| IL (1) | IL92778A0 (en) |
| WO (1) | WO1990006982A1 (en) |
| ZA (1) | ZA899838B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715375B2 (en) | 2007-09-27 | 2014-05-06 | Innospec Limited | Fuel compositions |
| WO2009040582A1 (en) * | 2007-09-27 | 2009-04-02 | Innospec Limited | Fuel compositions |
| EP2205702B1 (en) * | 2007-09-27 | 2017-03-08 | Innospec Limited | Fuel compositions |
| US8430936B2 (en) * | 2007-11-30 | 2013-04-30 | Baker Hughes Incorporated | Stabilization of fatty oils and esters with alkyl phenol amine aldehyde condensates |
| GB0903165D0 (en) | 2009-02-25 | 2009-04-08 | Innospec Ltd | Methods and uses relating to fuel compositions |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2696427A (en) * | 1951-01-26 | 1954-12-07 | Du Pont | Stabilized fuel oil compositions |
| US3060210A (en) * | 1960-05-12 | 1962-10-23 | Petrolite Corp | Polyaminomethyl phenols |
| US3269810A (en) * | 1963-09-19 | 1966-08-30 | Nalco Chemical Co | Antioxidants for cracked petroleum distillates, especially gasoline |
| US3649229A (en) * | 1969-12-17 | 1972-03-14 | Mobil Oil Corp | Liquid hydrocarbon fuels containing high molecular weight mannich bases |
| FR2370786A2 (en) * | 1976-11-12 | 1978-06-09 | Lubrizol Corp | IMPROVED AND COMBUSTIBLE DISPERSING AGENTS, LUBRICATING OILS AND CONCENTRATES CONTAINING THEM |
| US4166726A (en) * | 1977-12-16 | 1979-09-04 | Chevron Research Company | Diesel fuel containing polyalkylene amine and Mannich base |
| US4334085A (en) * | 1978-09-14 | 1982-06-08 | Standard Oil Company (Indiana) | Transamination process for Mannich products |
| EP0182940B1 (en) * | 1984-11-13 | 1990-04-11 | Mobil Oil Corporation | Mannich base oil additives |
| US4749468A (en) * | 1986-09-05 | 1988-06-07 | Betz Laboratories, Inc. | Methods for deactivating copper in hydrocarbon fluids |
-
1989
- 1989-11-30 JP JP2500892A patent/JPH03502819A/en active Pending
- 1989-11-30 EP EP90900593A patent/EP0403624A1/en not_active Withdrawn
- 1989-11-30 BR BR898907269A patent/BR8907269A/en unknown
- 1989-11-30 AU AU47488/90A patent/AU4748890A/en not_active Abandoned
- 1989-11-30 WO PCT/US1989/005411 patent/WO1990006982A1/en not_active Application Discontinuation
- 1989-12-15 CA CA002005707A patent/CA2005707A1/en not_active Abandoned
- 1989-12-18 IL IL92778A patent/IL92778A0/en unknown
- 1989-12-20 ES ES8904305A patent/ES2018123A6/en not_active Expired - Lifetime
- 1989-12-21 ZA ZA899838A patent/ZA899838B/en unknown
- 1989-12-21 CN CN89109812A patent/CN1044118A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IL92778A0 (en) | 1990-09-17 |
| WO1990006982A1 (en) | 1990-06-28 |
| BR8907269A (en) | 1991-03-12 |
| ZA899838B (en) | 1990-09-26 |
| CN1044118A (en) | 1990-07-25 |
| AU4748890A (en) | 1990-07-10 |
| JPH03502819A (en) | 1991-06-27 |
| EP0403624A1 (en) | 1990-12-27 |
| ES2018123A6 (en) | 1991-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5830243A (en) | Fuel compositions containing N-substituted perahydro-s triazines | |
| US5254138A (en) | Fuel composition containing a quaternary ammonium salt | |
| US3948619A (en) | Gasoline composition | |
| US6248142B1 (en) | Fuel composition containing lubricity additive | |
| US20060277820A1 (en) | Synergistic deposit control additive composition for gasoline fuel and process thereof | |
| CZ148598A3 (en) | Detergent additive for diesel fuel, diesel fuel preparation in which said additive is comprised, process of its preparation, method of removing sediments from diesel engine and method of preventing their formation | |
| AU619957B2 (en) | Middle distillate fuel having improved storage stability | |
| US3994698A (en) | Gasoline additive concentrate composition | |
| US3877889A (en) | Liquid hydrocarbon fuels containing Mannich bases or derivatives thereof | |
| WO1990010051A1 (en) | Fuel composition for control of intake valve deposits | |
| JPH07197052A (en) | Fuel composition and additive therefor | |
| US4581040A (en) | Polyoxyisopropylenediamine-acid anhydride-polyamine reaction product and motor fuel composition containing same | |
| CA1038851A (en) | Dispersant-detergent libricant and fuel additives | |
| EP0869163A1 (en) | Method for reducing engine friction | |
| US7422161B2 (en) | Treated port fuel injectors | |
| US4197091A (en) | Metal chelate/anti-oxidant combinations with dimer-trimer acids, pipeline corrosion inhibitors | |
| CA2005707A1 (en) | Fuel stabilizer composition | |
| US5266081A (en) | Multifunctional ashless dispersants | |
| EP0178960B1 (en) | Diesel fuel compositions | |
| US9650583B2 (en) | Additive and fuel compositions containing detergent and fluidizer and method thereof | |
| NZ231732A (en) | Fuel additive for combustion engines | |
| US3336384A (en) | Reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde | |
| US3236613A (en) | Petroleum distillates containing reaction products of amic acids and primary aliphatic amines with alkylene polyamines and salicylaldehyde | |
| CA2016580C (en) | Aliphatic diamines for distillate fuels stabilization | |
| GB2626637A (en) | Compositions, methods and uses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |