Classifications

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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
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  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/224—Amides; Imides carboxylic acid amides, imides
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
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  • C10L1/00—Liquid carbonaceous fuels
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  • 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
  • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

• This invention relates to fuel compositions for internal combustion engines which normally use low lead or unleaded gasoline.
• the fuels are further characterized as containing an alcohol.
• valve seat wear is a function - of engine design, load, speed conditions and operating temperature it is highly desirable that a replacement for lead be employed.
• the use of a lead replacement for valve seat recession is complicated by the fact that a number of newer vehicles do not require lead additives.
• a number of fuels on the market contain lower levels of lead and still other fuels are essentially lead-free.
• alcohol-containing fuels such as gasohol or - fuels containing alcohols used to boost octane rating are also widely marketed. It, therefore, becomes desirable to obtain a gasoline composition containing . a lead replacement which is capable of functioning in a multitude of gasoline based fuels.
• the metal may be selected from the Group la, Ila, Ilia, Va, lb, lib, Illb, IVb, Vb, Vlb, Vllb, VIII and tin.
• U.S. Patent 3,182,019 issued to Wilks et al on May 4, 1965, describes lubricating and fuel oils including complexes which contain an alkali or alkaline earth metal carbonate in colloidal form.
• the use of sodium in lead-free gasoline compositions for inhibiting valve seat recession is suggested in U.S. Patent 3,955,938 to Graham et al, issued on May 11, 1976.
• the sodium may be incorporated into the fuel in a number of different forms such as sodium derivatives or organic compounds which are soluble, or dispersed in the gasoline.
• simple sodium salts of an organic acid such as sodium petroleum sulfonate can be utilized although the sodium preferentially is added in the form of a sodium salt of an inorganic acid such as sodium carbonate in a colloidal dispersion in oil.
• Other convenient forms for introducing sodium into the fuel which are described in U.S. Patent 3,955,938 include various sodium salts of sulfonic acids, sodium salts of saturated and unsaturated carboxylic acids, sodium salts of phospho-sulfurized hydrocarbons such as may be prepared by reacting P 2 s c with petroleum fractions such as bright stock, and sodium salts of phenols and alkylphenols.
• Various optional additives described by the Graham patent include corrosion inhibitors, rust inhibitors, anti-knock compounds, anti-oxidants, solvent oils, anti-static agents, octane appreciators, e.g. t-butyl acetate, dyes, anti-icing agents, e.g. isopropanol, hexyleneglycol, ashless dispersants, detergents, and the like.
• the amount of sodium additive included in the fuel is an amount to provide from about 0.5 to 20, preferably 0.5 to 10 lbs. of sodium per 1000 barrels of gasoline (2.86g/1000 liters is 1 lb/1000 bbl) .
• gasoline compositions can be improved by including certain detergents and dispersants.
• Johnston et al discloses compositions containing a hydrocarbon-soluble alkali or alkaline earth metal- containing composition and a hydrocarbon-soluble ashless dispersant.
• the Johnston compositions are useful* for preventing valve seat recession.
• the present invention further describes a composition comprising: (A) at least one hydrocarbon-soluble or dis- persible alkali metal or alkaline earth metal containing composition,
• A a hydrocarbon-soluble or di ⁇ persible alkali earth metal or alkaline earth metal containing composition
• B at least one member selected from the group consist ⁇ ing of:
• the fuel compositions of the present invention will contain a minor amount of (A) at least one hydro ⁇ carbon-soluble alkali or alkaline earth metal-containing composition.
• A at least one hydro ⁇ carbon-soluble alkali or alkaline earth metal-containing composition.
• the presence of such metal-containing compositions in the fuel compositions of the present invention provides the fuel composition with a desirable ability to prevent or minimize valve seat recession in internal combustion engines, particularly when the fuel is an unleaded or low-lead fuel.
• the choice of the metal does not appear to be particularly critical although alkali metals are preferred, with sodium or potassium being the preferred alkali metals.
• the metal-containing composition (A) may be alkali metal or alkaline earth metal salts of sulfur acids, carboxylic acids, phenols and phosphorus acids. These salts can be neutral or basic. The former contain an amount of metal cation just sufficient to neutralize the acidic groups present in salt anion; the latter contain an excess of metal cation and are often termed overbased.
• These basic and neutral salts can be of oil-soluble organic sulfur acids such as sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulf ric, sulfurous and thiosulfuric acid. Generally they are salts of aliphatic or aromatic sulfonic acids.
• the sulfonic acids include the mono- or poly-nuclear aromatic or cycloaliphatic compounds.
• the sulfonic acids can be represented for the most part by the following formulae: Formula I Formula II in which T is an aromatic or " cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleum naphthenes,
• T is an aromatic or " cyclic nucleus such as, for example, benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine,
• R and R are each independently aliphatic groups, R contains at least
• R are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymerized C_ , C_ , C. , C j . , C fi , etc., olefins containing from about 15 to 7000 or more carbon atoms.
• the groups T, R 1 and R2 in the above formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc.
• the subscript x is generally 1-3, and the subscripts r + y generally have an average value of about 1-4 per molecule.
• oil soluble sulfonic acids coming within the scope of Formulae I and II above, and it is to be understood that such examples serve also to illustrate the salts of such sulfonic acids useful in this invention. ⁇ In other words, for every sulfonic acid enumerated it is intended that the corresponding neutral and basic metal salts thereof are also understood to be illustrate ' d.
• Such- sulfonic acids are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acids . derived from lubricating oil fractions having a Saybolt viscosity from about 100 seconds at 100°F
• the latter are acids derived from benzene which has been alkylated with propyl'ene tetramers or isobutene trimers to introduce 1, 2, 3 or more branched-chain C
• Dodecyl benzene bottoms principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufacturer of household detergents. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful in making the sulfonates used in this invention.
• LAS linear alkyl sulfonates
• the carboxylic acids from which "Suitable neutral and basic alkali metal and alkaline earth metal salts for use in this invention can be made include aliphatic, cyclo- aliphatic, and aromatic mono and polybasic carboxylic acids such as the naphthenic acids, alkyl- or alkenyl- substituted cyclopentanoic acids, the corresponding cyclohexanoic acids and the corresponding aromatic acids.
• the aliphatic acids generally contain at least eight carbon atoms and preferably at least twelve carbon atoms. Usually they have no more than about 400 carbon atoms. Generally, if the aliphatic carbon chain is branched, the acids are more oil soluble for any given carbon atom content.
• the cycloaliphatic and aliphatic carboxylic acids can be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, alpha-linolenic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecylic acid, dioctylcyclo- pentane carboxylic acid, myristic acid, dilauryldecahydro- naphthalene carboxylic acid, stearyl-octahydroindene carboxylic acid, palmitic acid, commercially available mixtures of two or more carboxylic acids such as tall oils acids, rosin acids, and the like.
• a group of oil-soluble carboxylic acids useful in preparing the salts used in the present invention are the oil-soluble aromatic carboxylic acids. These acids are represented by the general formula:
• R* is a hydrocarbyl (preferably aliphatic hydrocarbon-based) group of at least four carbon atoms, and no more " than about 400 aliphatic carbon atoms, a is an integer of from one to four, Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms, each X is independently a sulfur or oxygen atom, and m is an integer of from one to four with the proviso that R* and a are such that there is an average of at least 8 aliphatic carbon atoms provided by the R* groups for each acid molecule represented by Formula III.
• R* is a hydrocarbyl (preferably aliphatic hydrocarbon-based) group of at least four carbon atoms, and no more " than about 400 aliphatic carbon atoms
• a is an integer of from one to four
• Ar* is a polyvalent aromatic hydrocarbon nucleus of up to about 14 carbon atoms
• each X is independently a sulfur or oxygen atom
• m is an integer
• aromatic nuclei represented by the variable Ar* are the polyvalent aromatic radicals derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the like.
• the radical represented by Ar* will be a polyvalent nucleus derived from benzene or naphthalene such as phenylenes and naphthlene, e.g., methyl-phenylenes, ethoxyphenylenes, nitrophenylenes, isopropyl-phenylenes, hydroxyphenylenes, mercaptophenyl- enes, N,N-diethylaminophenylene ⁇ , chlorophenylenes, di- propoxynaphthylenes, triethylnaphthylenes, and similar • tri-, tetra-, pentavalent nuclei thereof, etc.
• phenylenes and naphthlene e.g., methyl-phenylenes, ethoxyphenylenes, nitrophenylenes, isopropyl-phenylenes, hydroxyphenylenes, mercaptophenyl- enes, N,N-dieth
• the R* groups are usually purely hydrocarbyl groups, preferably groups such as alkyl or alkenyl radicals.
• the hydrocarbon character is retained for purposes of this invention so long as any non-carbon atoms present in the R* group do not account for more than about 10% of the total weight of the R* groups.
• R* groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 2-hexenyl, cyclohexyloctyl,
• 5-methyloctyl and substituents derived from polymerized olefins such as polychloroprenes, polyethylenes, poly- propylenes, polyisobutylenes, ethylenepropylene co- polymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like.
• the group Ar may contain non-hydrocarbon substituents, for example, such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less than four carbon atoms, hydroxy, mercapto and the like.
• a group of particularly useful carboxylic acids are those of the formula:
• R*, X, Ar*, m and a are as defined in Formula III and p is an integer of 1 to 4, usually 1 or 2.
• p is an integer of 1 to 4, usually 1 or 2.
• R** in Formula V is an aliphatic hydrocarbon group containing at least 4 to about 400 carbon atoms
• Ph is a phenyl group
• a is an integer of from 1 to 3
• b is 1 or 2
• c is zero, 1, or 2 and preferably 1 with the proviso that R** and a are such that the acid molecules contain at least an average of about twelve aliphatic carbon atoms in the aliphatic hydrocarbon substituents per acid molecule.
• the aliphatic-hydrocarbon substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at least about sixteen carbon atoms per substituent and one to three substituents per molecule are particularly useful.
• Salts prepared from such salicylic acids wherein the aliphatic hydrocarbon substituents are derived from polymerized olefins, particularly polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, ethylene/ propylene co-polymers and the like and having average carbon contents of about 30 to 400 carbon atoms.
• carboxylic acids corresponding to Formulae III and IV above are well known or can be prepared according to procedures known in the art.
• Carboxylic acids of the type illustrated by the above formulae and processes for preparing their neutral and basic metal salts are well known and disclosed, for example, in such U.S. Patents as 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791.
• neutral and basic carboxylate salt used in this invention are those derived from alkenyl suceinates of the general formula:
• R* is as 'defined above in Formula III.
• Such salts and means for ' making them are set forth in U.S. Patents 3,271,130; 3,567,637 and 3,632,610.
• the molecular weight of the polybasic carboxylates will be about 400 to about 2000, preferably about 500 to about 1500.
• Such molecular weights will correspond to about 28 to about 145, preferably about 35 to about 110 carbon atoms in the hydrocarbon chain of the molecule.
• One such acid is propylene tetramer-substituted maleic acid.
• R*, a, Ar*, and m have the same meaning and preferences as described hereinabove with reference to Formula III. The same examples described with respect to Formula III also apply.
• a is an integer of 1-3, b is of 1 or 2 , z is 0 or
• Ph is a phenyl group
• R' in Formula VIII is a substantially saturated hydrocarbon-based substituent having an average of from about 30 to about 400 aliphatic
• R is selected from the group consisting of lower- alkyl, lower alkoxyl, nitro, and halo groups.
• phenates for use in this invention are the basic (i.e., overbased, etc.) alkali and alkaline earth metal sulfurized phenates made by sulfurizing a phenol and -described hereinabove with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Techniques for making these sulfurized phenates are described in U.S. Patents 2,680,096; 3,036,971 and 3,775,321.
• phenates that are useful are those that are made from phenols that have been linked through alkylene
• Alkali and alkaline earth metal salts of phosphorus acids also are useful in the fuel compositions of the invention.
• the normal and basic salts of the phosphonic and/or thiophosphonic acids prepared by reacting inorganic phosphorus reagents such as P ⁇ S,- with petroleum fractions such as bright stock or polyolefins obtained from olefins of 2 to 6 carbon atoms.
• polystyrenes having a molecular weight of from 700 to 100,000.
• Other phosphorus-containing reagents which have been reacted with olefins include phosphorus trichloride or phosphorus trichloride-sulfur chloride mixture, (e.g., U.S. Patent Nos. 3,001,981 and 2,195,517) , phosphites and phosphite chlorides (e.g., U.S. Patent Nos. 3,033,890 and 2,863,834) , and air or oxygen with a phosphorus halide (e.g., U.S. Patent No. 2,939,841) .
• the amount of alkali or alkaline earth metal containing composition (A) included in the fuel composition will be an amount which is sufficient to provide from about 1 to about 100 parts per million of the alkali metal or alkaline earth metal in the fuel composition.
• the amount of alkali metal or alkaline earth metal-containing composition (A) included in the fuel is an amount which is sufficient to reduce valve seat recession when the fuel is used in an internal combustion engine.
• a mixture of 1000 parts of a primary branched monoalkyl benzene sulfonic acid (M.W. , approximately 522) in 637 parts of mineral oil is neutralized with 145.7 parts of a 50% caustic soda solution and the excess water and caustic removed.
• the product containing the sodium salt obtained in this manner contains 2.5% sodium and 3.7% sulfur.
• Example A-3 The procedure of Example A-l is repeated except that the caustic soda is replaced by a chemically equivalent amount of Ca(OH) tract.
• Example A-3 The procedure of Example A-l is repeated except that the caustic soda is replaced by a chemically equivalent amount of Ca(OH)schreib.
• Example A-4 A mixture of 906 parts of an alkyl phenyl sulfonic acid (having an average molecular weight of 450, vapor phase osmometry) , 564 " parts mineral oil, 600 parts toluene, 98.7 parts magnesium oxide and 120 parts water is blown with carbon dioxide at a temperature of 78-85°C for seven hours at a rate of about 3 cubic feet of carbon dioxide per hour (85 1/hr) .
• the reaction mixture is constantly agitated throughout the carbonation. After carbonation, the reaction mixture is stripped to 165°C/20 torr (2.65 KPa) and the residue filtered.
• the filtrate is an oil solution of the desired overbased magnesium sulfonate having a metal ratio of about 3.
• Example A-5 A mixture of 906 parts of an alkyl phenyl sulfonic acid (having an average molecular weight of 450, vapor phase osmometry) , 564 " parts mineral oil, 600 parts to
• a mixture of 323 parts of mineral oil, 4.8 parts of water, 0.74 parts of calcium chloride, 79 parts of lime, and 128 parts of methyl alcohol is prepared, and warmed to a temperature of about 50°C.
• the mixture then is blown with carbon dioxide at a temperature of about 50°C at the rate of about 5.4 lbs. per hour (40.8g/minute) for about 2.5 hours.
• 102 additional parts of oil are added and the mixture is stripped of volatile materials at a temperature of about 150-155°C at 55 mm (7.3 KPa) pressure.
• the residue is filtered and the filtrate is the desired oil solution of the overbased calcium sulfonate having calcium content of about 3.7% and a metal ratio of about 1.7.
• the second component of the invention (B) is at least one member selected from the group consisting of: (i) a hydrocarbyl substituted sulfonated phenol or salt thereof;
• Component (B) (i) may be obtained by preparing the sulfonic acid of (B) (iii) or the salt of the sulfonic acid of B (iii) .
• An ample disclosure of the sulfonic acids and sulfonates is found in the description of component (A) .
• the cationic portion of (B) (i) is preferably ammonium.
• a phenol is employed as the aromatic nucleus in (A)
• the hydrocarbyl substituted phenol sulfonic acid or salt (B) (i) is obtained.
• the second item under (B) is an ethylene oxide/propylene oxide copolymer.
• Such materials are well known in the art and are obtained by reacting ethylene oxide or a polymer of ethylene oxide with propylene oxide or a polymer of propylene oxide. It is first possible to obtain a random polymer of ethylene oxide and propylene oxide by ' simply charging the desired quantities of each material and conducting the polymerization as- is known in the art. It is also possible to prepolymerize ethylene oxide to a desired chain length and then to furthe-r react the ethylene oxide by capping with propylene oxide. It is further possible to polymerize the propylene oxide to the desired molecular weight and to then terminate the propylene oxide polymer with ethylene oxide.
• the propylene oxide may be polymerized and then reacted with an ethylene oxide polymer.
• the molecular weight of (B) (ii) is conveniently about 400 to 10,000, preferably 600 to 5,000. It is desirable that the weight percent of the ethylene oxide in the copolymer is from 10 to 90 percent, preferably 15 to 90 percent by weight of the copolymer. It is, of course, recognized that as ethylene oxide has a lower molecular weight than propylene oxide that a greater number of equivalents of ethylene oxide will be utilized on a equivalent basis than of the propylene oxide.
• Component (iii) is a hydrocarbon substituted pTienol.
• the hydrocarbon substituted phenol generally corresponds to component (B) (i) the hydrocarbyl substituted sulfonated phenol or salt thereof.
• component (B) (iii) is usually the raw material for component (B) (i) and is commercially available.
• component (B) (iii) is usually the raw material for component (B) (i) and is commercially available.
• Either of components (B) (i) or (iii) will typically contain about 10 to about 30 carbon atoms on the hydrocarbyl chain on average, preferably about 14 to about 26 carbon atoms.
• the hydrocarbyl substituted phenol may also be crosslinked through the use of formaldehyde to give a polymeric structure. That is, the hydrocarbyl substituted phenol is crosslinked at the ortho (and often para position) to the hydroxyl groups. It is further possible to alkoxylate the phenol. In this regard, the reader's attention is directed to the discussion of ethylene oxide and propylene oxide given above. Each of the foregoing materials may be condensed onto the hycroxyl group of the phenol whether polymeric or mono eric.
• component (B) (iv)
• a preferre -' " . ' species of component (B) is, in fact, such a mixture.
• component (B) is (iv)
• the weight ratio of component (i) to (ii) is from about 10:1 to about 1:10, preferably about 5:1 to about 1:5.
• the weight ratio of (B) (i) to (B) (iii) is typically from about 8 : 1 to about 1:8, preferably about 5:1 to about 1:5.
• the desired ratio of component (B) (ii) to (iii) is typically about 7:1 to about 1:7, preferably 4:1 to about 1:4.
• the ratios are also as described above.
• the gasoline component (C) useful in the present invention is obtained as a hydrocarbon distillate.
• Gasolines are supplied in a number of different grades depending on the type of service for which they are intended.
• the gasolines utilized in the present invention include those designed as motor and aviation gasolines.
• Motor gasolines include those defined by ASTM specification D-439-73 and are composed of a mixture of various types of hydrocarbons including aromatics, olefins, .paraffins, isoparaffins , naphthenes and occasionally diolefins.
• Motor gasolines normally have a boiling range within the limits of about 20°C to 230°C while aviation gasolines have narrower boiling ranges, usually within the limits of about 37°C to 165°C.
• the gasoline may have any of the typically added ingredients provided that there are no adverse effects to obtaining performance for valve seat recession, obtaining the desired water fix, and which do not cause a substantial reduction of the octane value of the gasoline.
• One such ingredient which is typically included in gasoline is lead in the form of a compound such as tetraethyl lead or tetramethyl lead. It is first noted that lead is being regulated out of gasoline in many countries. Those countries still allowing some amounts of lead in the gasoline allow "low-lead" formulations. Typically, a low-lead gasoline contains less than about 0.5 gram of lead per gallon of fuel.
• This invention is concerned in one aspect with low-lead fuels containing as little as 0.1 gram of lead per gallon (0.0264 g/liter) of gasoline. It is further preferred in the present invention that the gasoline be lead-free.
• lead-free it is meant that small trace amounts of lead, significantly less than the amounts in a low-lead fuel, are tolerated. That is, - no-lead or lead-free gasoline compositions occasionally contain trace amounts of lead due to contamination by leaded fuels.
• no-lead or lead-free gasolines includes very small amounts of lead; however, it is preferred that the end gasoline product be completely lead-free.
• a further typical ingredient which is included with gasoline is a scavenger to remove or reduce engine deposits.
• the scavenger will be ethylene dichloride or ethylene dibromide or mixtures thereof.
• the reader is directed to U.S. Patent 4,690,687 issued September 1, 1987 to Johnston et al which " is herein incorporated by reference.
• THE ALCOHOL Alcohols (D) which are used in the present invention are typically those which are normally added to gasoline.
• the use of alcohols in gasolines is primarily for three purposes.
• the first purpose is as a partial fuel substitute for the hydrocarbons present in the gasoline to extend the supply of the petroleum hydrocarbons.
• methanol and ethanol are typically utilized as partial replacements for the hydrocarbon source in gasoline.
• the second group of alcohols often used in fuels are those alcohols which have utility as an octane enhancer.
• the octane enhancer alcohols will be materials such as methanol, ethanol, isopropanol, t-amyl alcohol and t-butanol.
• Such alcohols aid in the combustion of the hydrocarbon source and promote the clean burning of the fuel in the internal combustion engine cylinders, thereby 5 increasing power output.
• the alcohols which are typically employed in the present invention contain up to about 8 carbon atoms, preferably from about 1 to about 6 carbon atoms.
• the preferred alcohols for gasahol- production are methanol and
• the preferred alcohols for octane enhancement are tertiary alcohols.
• t-butanol is a preferred octane enhancer.
• An especially preferred combination of alcohols for use in octane enhancement is a mixture of t-butanol and methanol, particularly in a weight ratio to 0 "one another of 10:1 to 1:10, preferably about 5:1 to about 1:5.
• the level of usage of the alcohols in the present invention is typically from about 0.1 percent to about 45 percent by weight of the total gasoline composition. More 5 typically, the amount of alcohol present will be from about 0.5 percent to about 15 percent by weight of the total gasoline composition.
• the preferred alcohols for use in gasoline compositions of the present invention are monohydric 0 alcohols.
• the fuel compositions of the present invention desirably also contain a minor amount of (E) at least one hydrocarbon soluble ashless dispersant.
• the compounds 5 useful as ashless dispersants ⁇ enerally are characterized by a "polar" group attached to a relatively high molecular weight hydrocarbon chain.
• the "polar” group generally contains one or more of the elements nitrogen, oxygen and phosphorus.
• the solubilizing chains are generally higher in molecular weight than those employed with the metallic types, but in some instances they may be quite similar.
• any of the ashless detergents which are known in the art for use in lubricants and fuels can be utilized in the fuel compositions of the present invention.
• the dispersant is selected from the group consisting of
• the residual acylated polyamine has a nitrogen content of 4.7% by weight.
• Example E-4 To 1,133 parts of commercial diethylene triamine heated at 110-150°C is slowly added 6820 parts of isostearic acid over a period of two hours. The mixture is held at 150°C for one hour and then heated to 180°C over an additional hour. Finally, the mixture is heated to 205°C over 0.5 hour; throughout this heating, the mixture is blown with nitrogen to remove volatiles. The mixture is held at 205-230°C for a total of 11.5 hours and the stripped at 230°C/20 torr (2.65KPa) to provide the desired acylated polyamine as residue containing 6.2% nitrogen by weight.
• Example E-4 To 1,133 parts of commercial diethylene triamine heated at 110-150°C is slowly added 6820 parts of isostearic acid over a period of two hours. The mixture is held at 150°C for one hour and then heated to 180°C over an additional hour. Finally, the mixture is heated to 205°C over 0.5 hour; throughout this heating, the mixture is blown with nitrogen to remove volatiles. The
• Example E-5 To the cooled reaction mixture is added 100 parts toluene and 50 parts mixed butyl alcohols. The organic phase is washed three times with water until neutral to litmus paper and the organic phase filtered and stripped to 200°C/5-10 (0.66-1.33KPa) torr. The residue is an oil solution of the final product containing 0.45% nitrogen by weight.
• Example E-5 To the cooled reaction mixture is added 100 parts toluene and 50 parts mixed butyl alcohols. The organic phase is washed three times with water until neutral to litmus paper and the organic phase filtered and stripped to 200°C/5-10 (0.66-1.33KPa) torr. The residue is an oil solution of the final product containing 0.45% nitrogen by weight.
• Example E-5 To the cooled reaction mixture is added 100 parts toluene and 50 parts mixed butyl alcohols. The organic phase is washed three times with water until neutral to litmus paper and the organic phase filtered and stripped to 200°C/5-10 (0.66-1.33KPa
• a mixture of 140 parts of a mineral oil, 174 parts o a poly(isobutene) -substituted succinic anhydride (molecular weight 1000) having a saponification number cf 105 and 23 parts of isostearic acid is prepared at 90°C.
• a mixture of polyalkylene amines having an overall composition corresponding to that of tetraethylene pentamine at 80°-100°C throughout a period of 1.3 hours.
• the reaction is exothermic.
• the mixture is blown at 225°C with nitrogen at a rate of 5 pounds (2.27 Kg) per hour for 3 hours whereupon 47 parts of an aqueous distillate is obtained.
• Example E-6 A substantially hydrocarbon-substituted succinic anhydride is prepared by chlorinating a polyisobutene having a molecular weight of 1000 to a chlorine content of 4.5% and then heating the chlorinated polyisobutene with 1.2 molar proportions of maleic anhydride at a temperature of 150°-220°C.
• the succinic anhydride thus obtained has an acid number of 130.
• the dimethyl ester of the substantially hydrocarbon-substituted succinic anhydride of Example B-2 is prepared by heating a mixture of 2185 grams of the anhydride, 480 grams of methanol, and 1000 cc. of toluene at 50°-65°C while hydrogen chloride is bubbled through the reaction mixture for 3 hours. The mixture is then heated at 60°-65°C for 2 hours, dissolved in benzene, washed with water, dried and filtered. The filtrate is heated at
• Example E-8 A carboxylic ' " acid ester is prepared by slowly adding
• An ester is prepared by heating 658 parts of a carboxylic acid having an average molecular weight of 1018 (prepared by reacting chlorinated polyisobutene with acrylic acid) with 22 parts of pentaerythritol while maintaining a temperature of about 180°-205°C for about 18 hours during which time nitrogen is blown through the mixture. The mixture is then filtered and the filtrate is the desired ester. Further information on dispersants may be obtained from U.S. Patent 4,690,687 issued September 1, 1987 which is herein incorporated by reference.
• the amount of the hydrocabon-soluble or dispersible alkali metal . or alkaline earth metal-containing cc position (A) to the water fix (B) " is typically about
• the weight ratio of the water fix (B) to the ashless dispersant (E) is typically from about 2:1 to about 1:50, preferably about 1:1 to about 1:40.
• the amount of the ashless dispersant (E) to the gasoline is typically about 25 parts to about 500 parts, more preferably about 35 parts to 400 parts by weight of the dispersant per million parts of fuel.
• the weight ratio cf the hydrocarbon-soluble or dispersible alkali metal cr alkaline earth metal-containinc comoositicr: (A) to the ashless dispersant (E) is typically from about 4:0.1 to about 1:4.
• the amount of the hydrocarbon soluble alkali or alkaline earth metal-containing composition (A) included in the fuel compositions of the present invention may vary over a wide range although ' it is preferred not to include unnecessarily large excesses of the metal composition.
• the amount included in the fuel should be an amount sufficient to improve the desired properties such as the reduction of valve seat recession when the fuel is burned in internal combustion engines which are not designed for use with unleaded gas.
• the amount of metal composition to be included in the fuel will depend in part on the amount of lead in the fuel.
• unleaded fuels large amounts of the metal composition are required to provide the desirable reduction in valve seat recession.
• lesser amounts of the metal-containing composition generally are required.
• the amount of component (A) included in the fuel compositions of the present invention will be an amount which is sufficient to reduce valve seat recession when such fuels are utilized in an internal combustion engine.
• the fuel will contain less than about
• the fuel composition of the present invention will contain from about 1 to about 100 parts of the alkali metal or alkaline earth metal per million parts of fuel although amounts of from 5 to about 60 parts per million appear to be adequate for most applications.
• the amount of the hydrocarbon-soluble ashless dispersant optionally included in the fuel compositions of this invention also can vary over a wide range.
• the weight ratio of (B) the water fix to (E) the dispersant will be 2:1 to 1:50, preferably 1:1 to 1:40.
• the amount of (E) will depend in part on the amount of the metal-containing composition (A) .
• the ashless dispersant (E) is used at about 4:0.1 to about 1:10 by weight to (A) .
• the amount of the ashless dispersant to be included in the particular fuel composition can be determined readily by one skilled in the art and, obviously, the amount of dispersant contained in the fuel should not be so high as to have deleterious effects such as forming deposits on engine parts when the engine is cooled.
• Example 1 48.8 parts of mineral oil are added to a mixing vat having stirring capacity. A mixture of 0.6 parts of a "C Intel 4 alkylphenol sulfonate ammonium salt and 0.3 parts of a polyethylene glycol/polypropylene glycol copolymer having a molecular weight of 600 is added to the mixture. The copolymer is approximately 1:1 weight ratio of the monomers. A C Intel. substituted phenol is added at 0.3 parts by weight.
• Example E-2 To the foregoing mixture is added 8.4 parts of the ashless dispersant obtained from Example E-2. A fluidizing oil (high viscosity mineral oil) is added at 8 parts by weight. Lastly, 33.6 parts by weight of the active ingredient obtained from Example A-l are added to the mixture with stirring.
• a fluidizing oil high viscosity mineral oil
• the foregoing mixture is added at 250 PTB (pounds per thousand barrels or 0.71 g/1) to oxygenated gasoline as described below.
• the hydrocarbon component of the gasoline is 93.8%.
• the methanol is 3.89% and the t- butanol is 2.4% by weight.
• the respective volume ratio is ⁇ ⁇ - • ⁇ _ •
• the gasoline fuel is observed to have a high degree of water tolerance, e.g., any emulsification is quickly broken with substantially complete separation into ar. organic and a water phase.
• the product also functions to protect exhaust valve seats.
• This composition is formulated identically to Example 1, however, replacement of the sodium alkylbenzene sulfonate salt with an equivalent amount (on a sodium basis) of the neutral sodium salt of polyisobutylene succinic acid is employed. .
• the molecular weight of the anionic portion of the succinic acid salt is 950 and is obtained according to U.S. Patent 3,271,370 issued to Le
• the product is otherwise obtained as previously described in Example 1 and blended at the same level in gasoline.
• the product functions as an aid against valve seat recession and is observed to break aqueous emulsions rapidly.

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• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• 1989
  • 1989-01-10 AT AT89901780T patent/ATE107347T1/de not_active IP Right Cessation
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