CA2012559A1 - Stable middle distillate fuel-oil compositions - Google Patents
Stable middle distillate fuel-oil compositionsInfo
- Publication number
- CA2012559A1 CA2012559A1 CA002012559A CA2012559A CA2012559A1 CA 2012559 A1 CA2012559 A1 CA 2012559A1 CA 002012559 A CA002012559 A CA 002012559A CA 2012559 A CA2012559 A CA 2012559A CA 2012559 A1 CA2012559 A1 CA 2012559A1
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- CA
- Canada
- Prior art keywords
- middle distillate
- oil
- distillate fuel
- copolymer
- stable middle
- 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
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Abstract
STABLE MIDDLE DISTILLATE FUEL-OIL COMPOSITIONS
ABSTRACT OF THE INVENTION
A stable middle distillate fuel-oil composition which comprises (a) a major portion of a middle distillate fuel-oil; and (b) a minor amount, as a storage stabilizing additive, of N(4-anilinophenyl)succinimide of a copolymer and maleic anhydride graft.
ABSTRACT OF THE INVENTION
A stable middle distillate fuel-oil composition which comprises (a) a major portion of a middle distillate fuel-oil; and (b) a minor amount, as a storage stabilizing additive, of N(4-anilinophenyl)succinimide of a copolymer and maleic anhydride graft.
Description
20125~9 STABLE MIDDLE DISTILLATE E'UEL-OIL C~MPOSITIONS
(D#78, 907-F) BACKGROUND OF THE INVENTION
This invention relates to middle distillate fuels and, more particularly, to a storage stabilizing additive for a middle distillate fuel-heating oil composition.
In the manufacture and production of middle dis-tillate fuels and oils there is the problem of increased15 cracking of poorer quality crude oils. As a result, the commercially available diesel fuels and heating oils are less storage stable. Accordingly, stability additives are commonly introduced to prevent sludge formation and/or color change. However, to date these additives have not been effective or practical as to storage stabilizing middle distillates.
Thus, an object of the present invention is to provide a means of stabilizing efficiently a middle distil-late, e.g., diesel fuels and heating oil, in storage.
DISCLOSURE ST~TEMENT
U.S. Patent 4,089,794 discloses a process for preparing a lubricating oil concentrate of a VI improver having sludge dispersing properties wherein the VI improver is an ethylene copolymer with a number average molecular weight ranging from about 5,000 to 250,000 dissolved in a mineral lubricating oil.
- 20125~3 U.S. Patent 4,171,273 discloses a method of pre-paring fatty alkyl succinate ester and succinimide modified copolymers of ethylene and an ~g~p~a-olefin which are useful as shear stable visc.osity index (VI) improvers, dispersants and pour point dispersants in lubricating oils.
U.S. Patent 4,698,169 discloses additives useful in lubricant compositions having superior dispersant and antioxidant activity. The additives are products made by reacting (a) an alkenyl succinic compound with (b) an aryl-amine and (c) an alkanolamine or a hindered alcohol and borated reaction products thereof which provide dispersant and antioxidant activity to lubricant compositions.
SUMMARY OF THE INVENTION
This invention provides a stable middle distillate fuel-oil composition which comprises:
(a) a major portion of a middle distillate fuel-oil; and ~b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide of a copolymer and maleic anhydride graft of the formula H C ~ \
¦ N R
/C~/
(CP) o PR\VAM93 - 2 -2~125~9 wherein (CP) is a copolymer and R is ~CN)n H
R R"
where R'and R" are each aryl, alkylaryl, HN-Aryl, alkoxyl or H and n = 0 or 6.
DETAILED DESCRIPTION OF THE INVENTION
In providing the present fuel-oil composition, i.e., a stable middle distillate, a storage stabilizing agent is added to the middle distillate fuel-oil.
According to the present invention, the stable middle distillate fuel oil composition comprises:
(a) a major portion of a middle distillate fuel-oil; and (b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide 2S of a copolymer and maleic anhydride graft of the formula H2C / \
/ N --R
(CP) o/
PR\VAM93 - 3 -- 2û12559 wherein (CP) is a copolymer and R is ~ N
R R"
where R' and R" each are aryl, alkylaryl, HN-Aryl, alkoxyl or H and n = 0 or 6.
The polymer or copolymer substrate employed in the novel additive of the invention may be prepared from ethy-lene and propylene or it may be prepared from ethylene and ahigher olefin within the range of C3 to C10 alpha-monoole-fins.
More complex polymer substrates, often designated as interpolymers, may be prepared using a third component.
The third component generally used to prepare an interpoly-mer substrate is a polyene monomer selected from non-conju-gated dienes and trienes. The non-conjugated diene compo-nent is one having from 5 to 14 carbon atoms in the chain.
Preferably, the diene monomer is characterized by the pre-sence of a vinyl group in its structure and can include cyclic and bi-cyclo compounds. Representative ~ in- "~
clude 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbor,ene, 1,5- 'i~
heptadiene and 1,6-octadiene. A mixture of more than one diene can be used in the preparation of the interpolymer. A
preferred non-conjugated diene for preparing a terpolymer or interpolymer substrate is 1,4-hexadiene.
The triene component will have at least two non-conjugated double bonds and up to about 30 carbon atoms in the chain. Typtcal trienes useful in preparing the inter-PR\VAM93 4 polymer of the invention are l-isopropylidene-3a,4,7,7a-tetrahydroindene, l-isopropylidenedicyclopentadiene, dehydro-iso-dicyclopentadiene and 2-(2-methylene-4-methyl-3-pentenyl)-[2.2.1] bicyclo-5-heptene.
In the formulas above of the aromatic polyamines, R includes those and their isomers set forth below in Table 1.
Isomers of Polyamines N-phenylphenylenediamine N-phenylnaphthylenediamine N-naph,thylphenylenediamine N-4-an~lino-N'-phenylphenylenediamine '~ ~
The polymerization reaction to form the polymer substrate is generally carried out in the presence of a catalyst in a solvent medium. The polymerization solvent may be any suitable inert organic solvent that is liquid under reaction conditions for solution polymerization of monoolefins which is generally conducted in the presence of Ziegler type catalyst. Examples of satisfactory hydro-carbon solvents include straight chain paraffins having from 5-8 carbon atoms, with hexane being preferred. Aromatic hydrocarbons, preferably aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described above, are particularly suitable. The solvent selected may be a mix-ture of one or more of the foregoing hydrocarbons. It is desirable that the solvent be free of substances that will 35 interfere with Ziegler ~l~ori~ion reaction. ~c PR\VAM93 - 5 -2012a59 In a typical preparation of a polymer substrate, hexane is first introduced into a reactor and the tempera-ture in the reactor is raised moderately to about 30~C. Dry propylene is fed to the reactor until the pressure reaches about 40-45 inches of mercury. The pressure is then in-creased to about 60 inches of mercury and dry ethylene and 5-ethylidene-2-norbornene are fed to the reactor. The monomer feeds are stopped and a mixture of aluminum sesqui-chloride and vanadium oxytrichloride are added to initiate the plS~ on reaction. Completion of the polymeriza-tion reaction is evidenced by a drop in the pressure in the reactor.
Ethylene-propylene or higher alpha monoolefin lS copolymers may consist of from about 15 to 80 mole percent ethylene and from about 20 to 85 mole percent propylene or higher monoolefin with the preferred mole ratios being from about 25 to 75 mole percent ethylene and from about 25 to 75 mole percent of a (C3 to C10) alpha monoolefin with the most preferred proportions being from 25 to 55 mole percent ethylene and 45 to 75 mole percent propylene.
Terpolymer variations of the foregoing polymers may contain from about 0.1 to 10 mole percent of a non-conjugated diene or triene.
The polymer substrate, that is the ethylene copo-lymer or terpolymer, is an oil-soluble substantially linear, rubbery material having ~average mole~cular weight from ~ J
about 5,000 to 500,000 with a prefer ~ molecular weight range of 25,000 to 250,000 and a most preferred range from about 50,000 to 150,000.
The terms polymer and copolymer are used generi-cally to encompass ethylene copolymers, terpolymers or PR\VAM93 - 6 -2012~
interpolymers. These materials may contain minor amounts of other olefinic monomers so long as their basic characteris-tics are not materially changed.
An ethylenically unsaturated carboxylic acid material is next grafted onto the prescribed polymer back-bone. The materials which are attached to the polymer contain at least one ethylenic bond and at least one, pre-ferably two, carboxylic acid or its anhydride groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or a deriva-tive thereof is preferred. It grafts onto the ethylene copolymer or terpolymer to give two carboxylic acid func-tionalities. Examples of additional unsaturated carboxylic materials include chlormaleic anhydride, itaconic anhydride or the corresponding dicarboxylic a~ids such as maleic acid, fumaric acid and their monoesters.
The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer backbone in a number of ways. It may be grafted onto the backbone by a thermal process known as the "ene" process or by grafting in solution or in solid form using a radical initiator. The free-radical induced grafting of ethylenically unsaturated carboxylic acid materials in solvents such as benzene is a preferred method. It is carried out at an elevated temperature in the range of about 100C to 250C, preferably 120C to 190C and more preferably at 150C to 180C, e.g., above 160~C, in a solvent, preferably a mineral lubricating oil solution containing, e.g., 1 to 50, preferably 5 to 30 wt.~, based on the initial total oil solution, of the ethy-lene polymer and preferably under an inert environment.
The free-radical initiators which may be used are peroxides, hydroperoxides and azo compounds and, preferably, PR\VAM93 7 2~25~
those which have a boiling point greater than about 100C
and decompose thermally within the grafting temperature range to provide free radicals. Representative of these free-radical initiators are azobutyronitrile and 2,5-dimethyl-hex-3-yne-2,s bis-tertiary-butyl peroxide. The initiator is used in an amount of between about 0.005% and about 1 wt.% based on the weight of the reaction mixture solution~ The grafting is preferably carried out in an inert atmosphere, such as under nitrogen blanketing. The resulting polymer intermediate is characterized by having carboxylic acid acylating functions within its structure.
In the solid or melt process for forming a graft polymer, the unsaturated carboxylic acid with the optional use of a radical initiator is grafted on molten rubber using rubber masticating or shearing equipment. The temperature of the molten material in this process may range from about 150-400C.
Polymer substrates or interpolymers are available commercially. Particularly useful are those containing from bout 40 to about 60 mole percent ethylene units, about 60 to about 40 mole percent propylene units. Examples are "Ortholeum 2052" and "PL-1256" availble from E.I. duPont deNemours and Co. The former is a terpolymer containing about 48 mole percent ethylene units, 48 mole percent propylene units and 4 mole percent, 1,4-heaxdiene units, having an inherent viscosity of 1.35. The latter is a similar polymer with an inherent viscosity of 1.95. The viscosity average molecular weights of the two are on the order of 200,000 and 280,000 respectively.
Specifically and, more preferably, the copolymer may consist of ethylene and a (C3-C18) alpha-monoolefin.
PR\VAM~3 - 8 -2012~
As an additive that is an efficient storage stable stablizer for middle distillate fuel-heating oils, the poly ethylene-propylene succinimide derived from N-phenylph~nyl- J ~7/~
enediamine has the formula EP Copolymer ~ ~ NN
In determining the effectiveness of the stabilizer additive of the present invention, the preferred additive was compared with a commercially available dispersant stabi-lizer. The test performed is as discussed below.
METHOD OF TEST FOR POTENTIAL DEPOSIT TEST
FOR MIDDLE DISTILLATE FUELS
SCOPE
1. This method describes a procedure for predict-ing the storage stability of middle distillate fuels based on the amount of insoluble material formed under accelerated oxidizing conditions. The method is intended for use with 2S freshly produced fuels.
OUTLINE OF METHOD
2. The fuel sample is heated for two hours at 275F while air is being bubbled through the fuel at a rate of 3 liters per hour. At the end of the heating period the fuel is cooled at 77F for one hour and filtered through a 9.6 sq.cm. area of a No.l Whatman filter paper. The density ' of the insoluble material deposited f~r the filter paper is PR\VAM93 - 9 ~
2012~9 visually compared to the deposit code which has been corre-lated with actual field test results.
PREPARATION OF ETHYLENE PROPYLENE lEP) COPOLYMER DERIVATIVE
[EP: Ethylene Propylene ~ ~ Mol. Wt. ~j7/~, ~7/
80,000) MA graft level on EP is approximately 1.5 wt.%]
- EXAMPLE I
PROCEDURE ~PPDA) 1. Dissolve 70 g of MA-EP in 513 g of SNO-100 base oil at 160C under N2 blanket.
2. Stir 2 hours at 160C under N2.
3. Add a solution of 2.0 g of N-phenylphenylenediamine dissolved in 13 gms of surfonic N-40 (ethoxylated alkyl phenol solvent) and react for 2 hours at 160~C under N2 (low flow rate).
(D#78, 907-F) BACKGROUND OF THE INVENTION
This invention relates to middle distillate fuels and, more particularly, to a storage stabilizing additive for a middle distillate fuel-heating oil composition.
In the manufacture and production of middle dis-tillate fuels and oils there is the problem of increased15 cracking of poorer quality crude oils. As a result, the commercially available diesel fuels and heating oils are less storage stable. Accordingly, stability additives are commonly introduced to prevent sludge formation and/or color change. However, to date these additives have not been effective or practical as to storage stabilizing middle distillates.
Thus, an object of the present invention is to provide a means of stabilizing efficiently a middle distil-late, e.g., diesel fuels and heating oil, in storage.
DISCLOSURE ST~TEMENT
U.S. Patent 4,089,794 discloses a process for preparing a lubricating oil concentrate of a VI improver having sludge dispersing properties wherein the VI improver is an ethylene copolymer with a number average molecular weight ranging from about 5,000 to 250,000 dissolved in a mineral lubricating oil.
- 20125~3 U.S. Patent 4,171,273 discloses a method of pre-paring fatty alkyl succinate ester and succinimide modified copolymers of ethylene and an ~g~p~a-olefin which are useful as shear stable visc.osity index (VI) improvers, dispersants and pour point dispersants in lubricating oils.
U.S. Patent 4,698,169 discloses additives useful in lubricant compositions having superior dispersant and antioxidant activity. The additives are products made by reacting (a) an alkenyl succinic compound with (b) an aryl-amine and (c) an alkanolamine or a hindered alcohol and borated reaction products thereof which provide dispersant and antioxidant activity to lubricant compositions.
SUMMARY OF THE INVENTION
This invention provides a stable middle distillate fuel-oil composition which comprises:
(a) a major portion of a middle distillate fuel-oil; and ~b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide of a copolymer and maleic anhydride graft of the formula H C ~ \
¦ N R
/C~/
(CP) o PR\VAM93 - 2 -2~125~9 wherein (CP) is a copolymer and R is ~CN)n H
R R"
where R'and R" are each aryl, alkylaryl, HN-Aryl, alkoxyl or H and n = 0 or 6.
DETAILED DESCRIPTION OF THE INVENTION
In providing the present fuel-oil composition, i.e., a stable middle distillate, a storage stabilizing agent is added to the middle distillate fuel-oil.
According to the present invention, the stable middle distillate fuel oil composition comprises:
(a) a major portion of a middle distillate fuel-oil; and (b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide 2S of a copolymer and maleic anhydride graft of the formula H2C / \
/ N --R
(CP) o/
PR\VAM93 - 3 -- 2û12559 wherein (CP) is a copolymer and R is ~ N
R R"
where R' and R" each are aryl, alkylaryl, HN-Aryl, alkoxyl or H and n = 0 or 6.
The polymer or copolymer substrate employed in the novel additive of the invention may be prepared from ethy-lene and propylene or it may be prepared from ethylene and ahigher olefin within the range of C3 to C10 alpha-monoole-fins.
More complex polymer substrates, often designated as interpolymers, may be prepared using a third component.
The third component generally used to prepare an interpoly-mer substrate is a polyene monomer selected from non-conju-gated dienes and trienes. The non-conjugated diene compo-nent is one having from 5 to 14 carbon atoms in the chain.
Preferably, the diene monomer is characterized by the pre-sence of a vinyl group in its structure and can include cyclic and bi-cyclo compounds. Representative ~ in- "~
clude 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbor,ene, 1,5- 'i~
heptadiene and 1,6-octadiene. A mixture of more than one diene can be used in the preparation of the interpolymer. A
preferred non-conjugated diene for preparing a terpolymer or interpolymer substrate is 1,4-hexadiene.
The triene component will have at least two non-conjugated double bonds and up to about 30 carbon atoms in the chain. Typtcal trienes useful in preparing the inter-PR\VAM93 4 polymer of the invention are l-isopropylidene-3a,4,7,7a-tetrahydroindene, l-isopropylidenedicyclopentadiene, dehydro-iso-dicyclopentadiene and 2-(2-methylene-4-methyl-3-pentenyl)-[2.2.1] bicyclo-5-heptene.
In the formulas above of the aromatic polyamines, R includes those and their isomers set forth below in Table 1.
Isomers of Polyamines N-phenylphenylenediamine N-phenylnaphthylenediamine N-naph,thylphenylenediamine N-4-an~lino-N'-phenylphenylenediamine '~ ~
The polymerization reaction to form the polymer substrate is generally carried out in the presence of a catalyst in a solvent medium. The polymerization solvent may be any suitable inert organic solvent that is liquid under reaction conditions for solution polymerization of monoolefins which is generally conducted in the presence of Ziegler type catalyst. Examples of satisfactory hydro-carbon solvents include straight chain paraffins having from 5-8 carbon atoms, with hexane being preferred. Aromatic hydrocarbons, preferably aromatic hydrocarbon having a single benzene nucleus, such as benzene, toluene and the like; and saturated cyclic hydrocarbons having boiling point ranges approximating those of the straight chain paraffinic hydrocarbons and aromatic hydrocarbons described above, are particularly suitable. The solvent selected may be a mix-ture of one or more of the foregoing hydrocarbons. It is desirable that the solvent be free of substances that will 35 interfere with Ziegler ~l~ori~ion reaction. ~c PR\VAM93 - 5 -2012a59 In a typical preparation of a polymer substrate, hexane is first introduced into a reactor and the tempera-ture in the reactor is raised moderately to about 30~C. Dry propylene is fed to the reactor until the pressure reaches about 40-45 inches of mercury. The pressure is then in-creased to about 60 inches of mercury and dry ethylene and 5-ethylidene-2-norbornene are fed to the reactor. The monomer feeds are stopped and a mixture of aluminum sesqui-chloride and vanadium oxytrichloride are added to initiate the plS~ on reaction. Completion of the polymeriza-tion reaction is evidenced by a drop in the pressure in the reactor.
Ethylene-propylene or higher alpha monoolefin lS copolymers may consist of from about 15 to 80 mole percent ethylene and from about 20 to 85 mole percent propylene or higher monoolefin with the preferred mole ratios being from about 25 to 75 mole percent ethylene and from about 25 to 75 mole percent of a (C3 to C10) alpha monoolefin with the most preferred proportions being from 25 to 55 mole percent ethylene and 45 to 75 mole percent propylene.
Terpolymer variations of the foregoing polymers may contain from about 0.1 to 10 mole percent of a non-conjugated diene or triene.
The polymer substrate, that is the ethylene copo-lymer or terpolymer, is an oil-soluble substantially linear, rubbery material having ~average mole~cular weight from ~ J
about 5,000 to 500,000 with a prefer ~ molecular weight range of 25,000 to 250,000 and a most preferred range from about 50,000 to 150,000.
The terms polymer and copolymer are used generi-cally to encompass ethylene copolymers, terpolymers or PR\VAM93 - 6 -2012~
interpolymers. These materials may contain minor amounts of other olefinic monomers so long as their basic characteris-tics are not materially changed.
An ethylenically unsaturated carboxylic acid material is next grafted onto the prescribed polymer back-bone. The materials which are attached to the polymer contain at least one ethylenic bond and at least one, pre-ferably two, carboxylic acid or its anhydride groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. Maleic anhydride or a deriva-tive thereof is preferred. It grafts onto the ethylene copolymer or terpolymer to give two carboxylic acid func-tionalities. Examples of additional unsaturated carboxylic materials include chlormaleic anhydride, itaconic anhydride or the corresponding dicarboxylic a~ids such as maleic acid, fumaric acid and their monoesters.
The ethylenically unsaturated carboxylic acid material may be grafted onto the polymer backbone in a number of ways. It may be grafted onto the backbone by a thermal process known as the "ene" process or by grafting in solution or in solid form using a radical initiator. The free-radical induced grafting of ethylenically unsaturated carboxylic acid materials in solvents such as benzene is a preferred method. It is carried out at an elevated temperature in the range of about 100C to 250C, preferably 120C to 190C and more preferably at 150C to 180C, e.g., above 160~C, in a solvent, preferably a mineral lubricating oil solution containing, e.g., 1 to 50, preferably 5 to 30 wt.~, based on the initial total oil solution, of the ethy-lene polymer and preferably under an inert environment.
The free-radical initiators which may be used are peroxides, hydroperoxides and azo compounds and, preferably, PR\VAM93 7 2~25~
those which have a boiling point greater than about 100C
and decompose thermally within the grafting temperature range to provide free radicals. Representative of these free-radical initiators are azobutyronitrile and 2,5-dimethyl-hex-3-yne-2,s bis-tertiary-butyl peroxide. The initiator is used in an amount of between about 0.005% and about 1 wt.% based on the weight of the reaction mixture solution~ The grafting is preferably carried out in an inert atmosphere, such as under nitrogen blanketing. The resulting polymer intermediate is characterized by having carboxylic acid acylating functions within its structure.
In the solid or melt process for forming a graft polymer, the unsaturated carboxylic acid with the optional use of a radical initiator is grafted on molten rubber using rubber masticating or shearing equipment. The temperature of the molten material in this process may range from about 150-400C.
Polymer substrates or interpolymers are available commercially. Particularly useful are those containing from bout 40 to about 60 mole percent ethylene units, about 60 to about 40 mole percent propylene units. Examples are "Ortholeum 2052" and "PL-1256" availble from E.I. duPont deNemours and Co. The former is a terpolymer containing about 48 mole percent ethylene units, 48 mole percent propylene units and 4 mole percent, 1,4-heaxdiene units, having an inherent viscosity of 1.35. The latter is a similar polymer with an inherent viscosity of 1.95. The viscosity average molecular weights of the two are on the order of 200,000 and 280,000 respectively.
Specifically and, more preferably, the copolymer may consist of ethylene and a (C3-C18) alpha-monoolefin.
PR\VAM~3 - 8 -2012~
As an additive that is an efficient storage stable stablizer for middle distillate fuel-heating oils, the poly ethylene-propylene succinimide derived from N-phenylph~nyl- J ~7/~
enediamine has the formula EP Copolymer ~ ~ NN
In determining the effectiveness of the stabilizer additive of the present invention, the preferred additive was compared with a commercially available dispersant stabi-lizer. The test performed is as discussed below.
METHOD OF TEST FOR POTENTIAL DEPOSIT TEST
FOR MIDDLE DISTILLATE FUELS
SCOPE
1. This method describes a procedure for predict-ing the storage stability of middle distillate fuels based on the amount of insoluble material formed under accelerated oxidizing conditions. The method is intended for use with 2S freshly produced fuels.
OUTLINE OF METHOD
2. The fuel sample is heated for two hours at 275F while air is being bubbled through the fuel at a rate of 3 liters per hour. At the end of the heating period the fuel is cooled at 77F for one hour and filtered through a 9.6 sq.cm. area of a No.l Whatman filter paper. The density ' of the insoluble material deposited f~r the filter paper is PR\VAM93 - 9 ~
2012~9 visually compared to the deposit code which has been corre-lated with actual field test results.
PREPARATION OF ETHYLENE PROPYLENE lEP) COPOLYMER DERIVATIVE
[EP: Ethylene Propylene ~ ~ Mol. Wt. ~j7/~, ~7/
80,000) MA graft level on EP is approximately 1.5 wt.%]
- EXAMPLE I
PROCEDURE ~PPDA) 1. Dissolve 70 g of MA-EP in 513 g of SNO-100 base oil at 160C under N2 blanket.
2. Stir 2 hours at 160C under N2.
3. Add a solution of 2.0 g of N-phenylphenylenediamine dissolved in 13 gms of surfonic N-40 (ethoxylated alkyl phenol solvent) and react for 2 hours at 160~C under N2 (low flow rate).
4. Cool and screen filter (100 mesh).
The results of the test are provided below in Table I.
PR\VAM93 - 10 -2012~59 TABLE I
RESULTS OF POTENTIAL DEPOSIT TEST
Middle Distillate Results*
Base fuel (H-Oil Diesel Fraction) 3 ck 3 Base fuel + 60 PTB ECA 8477** 1 ck 1.5 Base Fuel + 60 PTB NPPDA (Ex.l) 1.5 ck 1.5 * The higher the number the poorer the stability of the ** A commercially available dispersant/stablizier for diesel fuel.
The test results of Table I above indicate that this additive stablizes the diesel fuel against~light-tem~ r~, perature oxidation and ~ ~-~ equivalent in a ~ to ~/
15 ~ commercially available additive~.
It should be noted that the description presented herein is intended to be merely illustrative of the present invention and not limiting in any manner. The scope of the invention, therefore, is to be determined by the appended claims.
PR\VAM93 - 11 -
The results of the test are provided below in Table I.
PR\VAM93 - 10 -2012~59 TABLE I
RESULTS OF POTENTIAL DEPOSIT TEST
Middle Distillate Results*
Base fuel (H-Oil Diesel Fraction) 3 ck 3 Base fuel + 60 PTB ECA 8477** 1 ck 1.5 Base Fuel + 60 PTB NPPDA (Ex.l) 1.5 ck 1.5 * The higher the number the poorer the stability of the ** A commercially available dispersant/stablizier for diesel fuel.
The test results of Table I above indicate that this additive stablizes the diesel fuel against~light-tem~ r~, perature oxidation and ~ ~-~ equivalent in a ~ to ~/
15 ~ commercially available additive~.
It should be noted that the description presented herein is intended to be merely illustrative of the present invention and not limiting in any manner. The scope of the invention, therefore, is to be determined by the appended claims.
PR\VAM93 - 11 -
Claims (6)
1. A stable middle distillate fuel-oil composi-tion comprising:
(a) a major portion of a middle distillate fuel-oil: and (b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide of a copolymer and maleic anhydride graft of the formula wherein (CP) is a copolymer and R is where R', R" are each aryl, alkylaryl, HN-Aryl, alkoxyl or H
and n = 0 or 6.
(a) a major portion of a middle distillate fuel-oil: and (b) a minor amount of, as a storage stabilizing additive, an aromatic polyamine succinimide of a copolymer and maleic anhydride graft of the formula wherein (CP) is a copolymer and R is where R', R" are each aryl, alkylaryl, HN-Aryl, alkoxyl or H
and n = 0 or 6.
2. The stable middle distillate fuel-oil compo-sition of Claim 1 wherein the copolymer consists of ethylene and a (C3-C18) alpha-monoolefin.
PR\VAM93 - 12 -
PR\VAM93 - 12 -
3. The stable middle distillate fuel-oil composition of Claim 1 wherein the copolymer has a number Avg. molecular weight ranging from about 5,000 to about 500,000.
4. The stable middle distillate fuel-oil compo-sition of Claim 1 wherein said composition is a diesel fuel/heating oil composition.
5. The stable middle distillate fuel-oil compo-sition of Claim 1 wherein said stabilizing additive is N (4-anilinophenyl) succinimide bound onto an ethylene-propylene copolymer.
6. The stable middle distillate fuel-oil compo-sition of Claim 1 wherein said alkyl polytertiary amine is selected from the group consisting of all isomers of N-phe-nylphenylenediamine, N-phenylnaphthylenediamine, N-naphthyl-phenylenediamine and N-4-anilino-N'-phenylphenylenediamine PR\VAM93 - 13 -
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002012559A CA2012559A1 (en) | 1989-08-03 | 1990-03-20 | Stable middle distillate fuel-oil compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/389,158 US5000759A (en) | 1988-12-22 | 1989-08-03 | Stable middle distillate fuel-oil compositions |
| CA002012559A CA2012559A1 (en) | 1989-08-03 | 1990-03-20 | Stable middle distillate fuel-oil compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2012559A1 true CA2012559A1 (en) | 1991-09-20 |
Family
ID=25674020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012559A Abandoned CA2012559A1 (en) | 1989-08-03 | 1990-03-20 | Stable middle distillate fuel-oil compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2012559A1 (en) |
-
1990
- 1990-03-20 CA CA002012559A patent/CA2012559A1/en not_active Abandoned
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| Date | Code | Title | Description |
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| FZDE | Discontinued |