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

Definitions

• This invention relates to an improvement in hydrocarbon fuels, and particularly hydrocarbon distillate fuels, to the extent that they are stabilized against deposit formation under varying conditions of static and dynamic flow incident to ultimate introduction into a combustion zone.
• the deposit-forming tendencies of hydrocarbon fuels, and particularly the petroleum distillate fuels, are largely dependent upon their composition and the conditions to which they are subjected prior to energy-release through combustion in a combustion zone.
• Cornpositionwise, the deposit-forming tendencies or instability of the fuel are usually associated with the presence of thermally and/ or catalytically cracked components in the fuel and become increasingly pronounced in the higher boiling range fuels.
• certain conditions of storage, transportation and service prior to combustion also contribute materially to the deposit forming tendencies of the fuel. These conditions are generally conditions of oxidation and result in the formation of soluble and insoluble oxidation products which form the bulk of the deposits laid down on the various metal and other surfaces within the fuel system.
• the presence of nonhydro'oarbon contaminants in the fuel, and particularly metals such as copper and iron accelerates the oxidative reactions and coincident deposit formation.
• oxidative deterioration is obtained as a low temperature oxidation during storage in the presence or" air, and the resulting deposit formation is substantially dependent upon the composition or stability of the fuel.
• Other types of oxidative conditions which, in addition, promote deposit formation are encountered in the conditions and fuel systems specific to the various types of hydrocarbon fuels.
• deposit formation is encountered within the induction system and particularly at the intake valves, injector nozzles, and injection plungers.
• the hydrocarbon fuel is subjected to comparatively high temperatures and comes in contact with combustion and exhaust gases containing oxidation precursors, etc.
• the class of copolymer compositions which have been determined to be unique in these improving characteristics may be defined as a relatively high molecular weight copolymer which may be obtained by the copolymerization of (A) at least one compound containing an ethylenic linkage and 8 to 30 aliphatic or cycloaliphatic carbon atoms which is copolymerizable through the ethylenic linkage, and (B) at least one compound of the group of il-unsaturated dicarboxylic acids or acid anhydrides, which copolymer is so constituted that the ratio of (A) to (B) is within the range of 1 to 15 and in which 0 to 90 percent of the available carboxyl groups of component (B) are present in the form of their ester, amide, imide, and/or amine salt derivatives.
• the particular composition chosen for optimum effectiveness is dependent largely upon the particular type of hydrocarbon fuel, its composition, and the environmental conditions to which the fuel is subjected prior to introduction into a combustion zone.
• the' specific copolymer composition employed in a motor gasoline for maximum effectiveness in reducing the intake manifold deposits in a spark-ignition, internal combustion engine Will usually differ chemically Within the foregoing classification from the copolymer additives inconporated in a high-boiling burner fuel containing large concentrations of cracked gas oil to eifect the maximum reduction in clogging and plugging of filters, screens, pumps, and the like.
• carboxyl groups are intended to include the dehydrated carboxyl groups present in the acid anhydrides and which are reactive for the purpose of forming the ester, amide, imide, or amine salt derivatives.
• the copolymerizable component (A), as previously defined, is primarily employed to impart the required degree of oil solubility to the copolymer composition and is preferably a neutral O-polar compound containing 8 to 30 aliphatic carbon atoms with a copolymerizable ethylenic linkage alpha or beta to the polar group.
• the copolymerizable component (A) may be defined as a compound having the general formula:
• R CI-I CH(CH -QR where R maybe hydrogen or an acyclic hydrocarbon, Q may be oxygen or a carbonyl-oxy iO or O( i-) radical, R is an acyclic hydrocarbon radical having from 8 to 20 carbon atoms, and x may be 0 or 1.
• the component (A) is desirably one or more aliphatic esters containing 8 to 30 carbon atoms and a copolyrnerizable ethylenic linkage alpha or beta to the carboxyl group.
• component (A) includes the following: olefin hydrocarbons and particularly alkenes such as polyisobutylene and dodecene-l; cycloal'kenes such as cyclohexene, 4-octylcyclo- -hexene-1, and vinylcyclohexane; and styrenes such as poctylstyrene and p-t-butylstyrene; olefinic ethers, representative of which are the vinyl ethers such as vinyl nbutyl ether, vinyl 2-ethylhexyl ether and vinyl p-octylphenyl ether; allyl ethers such as allyl cyclohexyl ether and allyl isobutyl ether; and methallyl ethers such as methallyl n-hexyl ether and meth-ally
• the other copolymerizable component identified for convenience as component (B), is employed for the purpose of supplying the requisite active polar constituents in the copolymer composition.
• component (B) is employed for the purpose of supplying the requisite active polar constituents in the copolymer composition.
• component (B) consists of a dicarboxylic acid or anhydride with a copolymerizable olefinic linkage in the 01$ position to at least one of the can lected from the aliphatic dicarboxylic acids and anhydrides and preferably the cap-unsaturated dicarboxylic acids and More specifically, componentlB) is se- ⁇ in which R and R are either hydrogen or lower alkyl radicals and G is oxygen, in the case of the acid anhydride, or two OH radicals, in the case of the free dicarboxylic acid. 1
• component (B) Representative of the acids and anhydrides included within the preferred classification of component (B) are maleic acid and its anhydride, itaoonic acid and its anhydride, citraconic acid and its anhydride, fumaric acid, and mesaconic acid, as well as the various substituted derivatives wherein the substituent groups do not interfere with the copolymerizing characteristics of the u,,8-unsaturated or olefinic linkage.
• component (B) has here been defined in terms of a free dicarboxylic acid or anhydride
• the final copolymer composition may present up to percent of the available carboxyl groups of component (B) in the form of their ester, amide, imide, and/or amine salt derivatives.
• These derivatives may be introduced initially into the copolymen'zation reaction by employing as the monomer (B) appropriate mixtures of the dicarboxylic acid derivatives and the free dicarboxylic acid and/ or anhydnide, or the copolymerization may be effected with the dicarboxylic acid or anhydride monomer and the resulting copolymer reacted with the panticular alcohol or amine in appropriate ratio to effect the desired degree of derivative formation.
• the desirability of modifying the basic copolymer structure through the use or by the formation of the carboxylic acid derivatives is primarily dependent upon the environmental conditions to which the compounded hydrocarbon fuel is subjected. In addition to the previous variables in hydrocarbon type and projected service conditions, a further selection of optimum copolymer composition is predicated upon the presence or absence of water in the fuel system, e.g., wet or dry fuel system. It has been found that, in general, the modified copolymers in which up to 90 percent of the available carboxyl groups in component (B) are presented in the form of their esterificd or aminated derivatives possess certain performance advantages when employed as an improving agent for hydrocarbon fuels in a wet fuel system.
• the derivatives contemplated within the scope of the invention are such derivatives as may be produced by conventional esterification or amination reactions with the available carboxyl groups of the dicarboxylic acids and/ or anhydrides or component (B).
• amination reactions is meant the generalized reactions of ammonia and its substituted derivatives, e.g., primary, secondary and tertiary amines, with a carboxyl group or an acid anhydride group, including the various stages of dehydration, e.g., amine salt, amide, imide, etc. formation.
• these derivatives may be initially presented as an integral function of the monomer (B) to the copolymerization reaction, it is preferred to conduct the copolymerization reaction with thefree dicarboxylic acid and/ or anhydride as the copolymerizable monomer (B) and subsequently modify the resulting copolymer by the csterification or amination reactions to introduce the particular J derivative functions in the desired degree.
• This preferred mode of preparation facilitates the conduct of the copolymerization reaction; yields a more uniform copolymer backbone; and permits more latitude in the degree of derivative formation.
• the type of derivatives which may be formed as contemplated by the invention is necessarily dependent upon the projected conditions of service and improvements desired.
• the ester and amide derivatives are preferred.
• the partial esterification may be conducted with aliphatic, cycloaliphatic, or aromatic monoand polyhydric alcohols, and the partial amination reactions with ammonia or monoand polyamines within a wide range of structural deviation and molecular weight.
• the following representative types of alcohols may be employed in the formation of the ester derivatives.
• the aliphatic alcohols containing usually from 1 to 18 carbon atoms such as the substituted and unsubstituted alcohols, are preferred although aromatic alcohols, as well as the alicyclic alcohols, such as cyclohexanol, pine oil, abietyl alcohol, etc., may be used.
• the polyhydric alcohols such as the glycols, glycerols, pentaerythritols, sorbitans, and polyalkylene glycols and their condensation products, have found merit.
• the polyethylene and polypropylene glycols either per se or in combination with varying molecular weights up to about 800, may be employed.
• the ethylene oxide condensation products with fatty amines, fatty acids, and fatty acid amides may also be used.
• esterifying alcohol has been noted, namely, that esterification with polyhydric alcohols and amino alcohols, for example glycols, polyalkylene glycols, and alkanolamines, may result in cross-linkage within the polymer structure, as evidenced by gel formation. Accordingly, it is preferred to avoid the presence of free active hydroxyl groups in the ester radical which is accomplished, in the case of the polyethylene glycols, by capping the residual or terminal hydroxyl radical.
• representative amines which may be employed to form the aminated derivatives include the monoand poly-functional amines as represented by the primary, secondary, and tertiary aliphatic, aromatic, or alicyclic amines, which preferably contain up to 18 carbon atoms, as well as the polyamines and poly-functional amines, including the amino acids, amino alcohols, amino phenols, polyalkylene polyamines, glyoxalidines or imidazolines and substituted derivatives thereof.
• the preparation of the copolymer improving agents involving the copolymerization of the monomers of component (A) and component (B) may be carried out according to the conventional bulk, solution or emulsion methods of polymerization, the choice of which will depend largely upon practical considerations and the particular types of monomers to be copolymerized. .Although considerable variation in ratio of component (A) and component (B) may be indulged, it has been found that the optimum performance characteristics of these copolymer improving agents, which may be represented as A B are obtained when the ratio of component (A) to component (B) lies within the range of from 1 to 15,
• the copolymerization reaction may be conducted in accordance with the conventional bulk, solution or emulsion methods of polymerization in the presence of a polymerization catalyst or initiator.
• an inert organic solvent such as benzene, toluene, Xylene orpetroleum naphtha, tofacilitate control of the reaction and handling of the resulting copolymer.
• copolymen'zation is preferably elfect'edin the presence with a cobalt 60 source.
• the organic catalyst or initiator may be employed in amounts of 0.1 to percent, and preferably in the range of 0.25 to 2 percent, which amounts may be incorporated in increments as the reaction proceeds.
• the temperature of copolymerization will vary, depending upon the selected monomeric reactants and solvent employed, and may vary from about 75 to 150 C.
• the copolymers formed may have a wide range of apparent molecular weight, and usually of the order of at last several thousands.
• the majority of the desired copolymer compositions to be employed as improving agents are substantially miscible in hydrocarbon oils, and may be compounded into additive concentrates of at least 10 percent by weight, and preferably up to 70 percent by weight.
• concentration of copolymer in the hydrocarbon vehicle such as toluene, mixed xylenes, kerosene, or other petroleum fractions, may be limited by the tendency toward gel formation, and in such instances it has been found desirable to incorporate a modifying agent or polar solvent, such as dimethyl formamide, tetrahydrofuran, Z-methyltetrahydrofuran, dioxane, cresylic acids, propylene carbonate, etc., which function as solubilizing agents and cosolvents in the copolymer concentrate.
• a modifying agent or polar solvent such as dimethyl formamide, tetrahydrofuran, Z-methyltetrahydrofuran, dioxane, cresylic acids, propylene carbonate, etc.
• modifying agents or cosolvents are generally employed in concentrations ranging from 1 to 25 percent of the concentrate.
• other conventional fuel additives which are compatible with the copolymer improving agent may be incorporated into the concentrate for the purpose of facilitating the handling and blending problems involved in the production of the finished hydrocarbon fuel.
• EXAMPLE 1 To a glass reaction flask equipped with stirring means, thermometer, reflux condenser and dropping funnel was charged 98 grams (1 mole) of maleic anhydride and 324 grams (1 mole) of allyl stearate along with about 10 cc. of benzene. The contents of the flask were heated to about 225 F. while stirring. About 6.3 grams of benzoyl peroxide dissolved in 100 cc. of benzene was added to the mixture over a period of about 4 hours. The temperature was maintained between about 200 and 230 F. by heating or cooling as necessary during the addition.
• reaction mixture was diluted with an equal volume of kerosene distillate and warmed under reduced pressure to remove the benzene, maleic anhydride, and the majority of the kerosene carrier. Distillation was continued to a bottoms temperature of 400 F. at 50 mm. mercury pressure (vapor line temperature 350 F.). The distillation bottoms consisted of a solution of copolymer in the higher boiling fractions of kero sene and included small amounts of unreacted lauryl methacrylate.
• EXAlVIPLE 3 The copolymerization reaction conducted in accordance with the procedure of Example 2 was repeated employing 1 mole (253 grams) of lauryl methacrylate, 0.255 mole (25 grams) of maleic anhydride, 0.7 gram of benzoyl peroxide, and 275 ml. of benzene.
• the resulting copolymer of lauryl methacrylate and maleic anhydride contained an approximate ratio of 6/1 or, in other words, A /B
• a copolymer concentrate of the lauryl methacrylatemaleic anhydride copolymer prepared in Example 2 (A /B was obtained by diluting the monomer-free copolymer to a 50 percent concentration in an aromatic petroleum distillate.
• esterification procedure was applied to the copolymer of Example 2 under varying degrees of esterification and employing varying types of alcohol reactants, including lauryl alcohol, isopropanol, capped and uncapped polyethylene glycols of varying molecular weights, abietyl alcohol, ethylene oxide condensation products with fatty acids of varying molecular weights, and ethylene oxide condensation products with fatty acid amides.
• alcohol reactants including lauryl alcohol, isopropanol, capped and uncapped polyethylene glycols of varying molecular weights, abietyl alcohol, ethylene oxide condensation products with fatty acids of varying molecular weights, and ethylene oxide condensation products with fatty acid amides.
• EXAMPLE 5 200 grams of the 50 percent concentrate of the copolymer of Example 2, together with grams of an aromatic petroleum solvent and 10.5 grams of dimethyl formamide, were charged to a reaction flask. The copolymer solution was heated to 200 F., and 15.7 grams of di-n-butylamine was added dropwise with stirring over a period of 1 hour. The agitation was continued at 250 F. for an additional 2 hours.
• the reaction mixture was the cooled and, on analysis by infrared adsorption, it was determined that the resulting composition contained 14.5 percent free available carboxyl groups or, conversely, 85.5 percent of the available carboxyl groups of the original co- EXAMPLE 6
• 200 grams of an unst-ripped copolymer reaction product which was taken from an aliquot from a copolymerization reaction conducted as in Example 2, was chargedto a reaction flask with 0.25 gram of benzoyl peroxide. The mixture was heated to reflux temperature (about 200 F.
• EXAMPLE 7 81 grams of allyl stearate, 49 grams of molten maleic anhydride, and 67 grams of lauryl methacrylate, together with 0.41 gram of benzoyl peroxide and 0.56 gram of t-butyl hydroperoxide, were charged with 10 ml. of benzene to a three-necked flask fitted with reflux and agitating means. The mixture was heated at 2052l0 F. with stirring for 85 hours with no apparent reaction. At this point, 0.97 gram of benzoyl peroxide was added. The temperature rose to 252 F. and thickening was visible. The reaction mixture was immediately cooled to 220 F. and heating continued at this temperature for 3 hours.
• an additional 500 ml. sample of the fuel is filtered through filter paper-into an unstopper l-quart bottle and stored at 140 F. for 4 weeks. At the end of this time, the sample is filtered through a tared Gooch crucible. The material adhering to the container is dissolved in 25 ml. of an /20 benzene-alcohol solution. The gums are precipitated by the addition of 500 m1. of petroleum ether, and the mixture is also filtered through the Gooch crucible. The crucible is then washed, dried and weighed as previous.
• the aging pro cedure is identical with the previous except that 10 ml. of distilled water is added to the l-quart bottle before the fuel is aged for 4 weeks at 140 F. At the end of this time, the 5 00 ml. of aged fuel is carefully decanted from the water layer and filtered, then the water layer is filtered through the same crucible, and the bottle is washed and the crucible weighed as before.
• filter residue test results were obtained on various base stocks employing an unmodified lauryl methacrylate-maleic anhydride copolymer in the-approximate ratio A /B wherein A designates the lauryl methacrylate component and B the maleic anhydride component.
• the base stocks were four No. 2 fuels (CS 12-48), identified in the following table, and the test was conducted in a dry system. a
• the representative .copolymer was a lauryl methacrylatemaleic 'anhydride copolymer'. in the approximate ratio.
• the base monomers of the copolymer will be identified for the sake of convenience according to the following code: Alaury1 methacrylate; A'-allyl stearate; A -methallyl stearate; and B-maleic anhydride; and the subscript following the respective monomer indicates the approximate mole ratio of the monomer in the copolymer backbone. Except as indicated in the table, the modifying reactants are reacted to form the corresponding derivatives of an estimated 50 percent of the available carboxyl groups in the basic copolymer.
• the fatty portion is coco amide in this case.
• x plus 1/ is a total of 5 moles ethylene oxide per mole of Ethomid 0/15.
• Ethomeen l8/25-a tertiary amine having a stearyl alkyl group and two polyoxyethylene groups substituted on the nitrogen of the generalformula:
• a combustible hydrocarbon fuel composition comprising a major portion of a hydrocarbon fuel and a minor portion, sufficient to reduce the deposit-forming characteristics of said fuel, of a relatively high molecular Weight copolymer obtained by the copolymerization of (A) monomers selected from the group consisting of aliphatic esters of monocarboxylic acid containing 8 to 30 carbon atoms and a single copolymerizable ethylenic linkage, said ethylenic linkage being alpha and beta to the carboxyl group, and (B) monomers selected from the group consisting of maleic acid and maleic anhydride in which the ratio of (A) to (B) is within the range of 1 to 15 and in which 15 to percent of the available carboxyl groups of (B) are present in the form of monoesters of polyalkylene glycols selected from the group consisting of polyethylene glycols having a molecular weight up to about 800 and monoalkyl ethers of said polyethylene glycols.
• a concentrate adapted to be incorporated inhydro carbon fuels in concentrations eifective to reduce the deposit-forming characteristics of said fuels consisting essentially of a hydrocarbon'vehicle containing from 10 to 70 percent by weight of a relatively high molecular weight copolymer obtained by copolymerization of (A) monomers selected from the group consisting of aliphatic esters of monocarboxylic acid containing 8 to 30 carbon atoms and a single copolymerizable ethylenic linkage, said ethylenic linkage being alpha and beta to the carboxyl group, and (B) monomers selected from the group consisting of maleic acid and maleic anhydride in which the ratio of (A) to (B) is Within the range of l to 15 and in which 15 to 90 percent of the available carboxyl groups of (B) are present in the form of monoesters of polyalkylene glycols selected from the group consisting of'polyethylene glycols having a molecular weight up to about 800
• a combustible hydrocarbon fuel composition comprising a major portion of a hydrocarbon fuel predominantly boiling above 250 F. and a minor portion, sufiicient to reduce the deposit-forming characteristics of said fuel, of a relatively high molecular weight copolymer produced through copolymerization of (A) dodecyl methacrylate and (B) maleic anhydride, in which copolymer the ratio of (A) to (B) is within the range of l to 15 and in which 15 to 90 percent of the available carboxyl groups of (B) are present in the form of monoesters of polyethylene glycol having a molecular weight of about 4.
• a combustible hydrocarbon fuel composition comprising a major portion of'a hydrocarbon fuel predominantly boiling above 250 F.
• a combustible hydrocarbon fuel composition comprising a major portion of a hydrocarbon fuel predominantly boiling above 250 F. and a minor portion, sufiicient to reduce the deposit-forming characteristics of said fuel, of a relatively high molecular Weight copolymer produced through copolymerization of (A) dodecyl methacrylate and (B) maleic anhydride, in which copolymer the ratio of (A) to (B) is about 4.5 to 1 and in which about 50 percent of the available carboxyl groups of (B) are present in the form of monoesters of polyethylene glycol having a molecular weight of about 200.
• a combustible hydrocarbon fuel composition comprising a major portion of a hydrocarbon fuel predominantly boiling above 250 F. and a minor portion, sufiicient to reduce the deposit-forming characteristics of said fuel, of a relatively high molecular weight oopolymer produced through copolymerization of (A) dodecyl methacrylate and (B) maleic anhydride, in which copolymer the ratio of (A) to (B) is about 4.5 to 1 and in which about 20 percent of the available carboxyl groups of (B) are presen in the form of monoesters of polyethylene glycol having a molecular Weight of about 400.

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• 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)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (12)

Citations (8)

• 0
  • BE BE546263D patent/BE546263A/xx unknown
• 1955
  • 1955-03-22 US US496076A patent/US3010810A/en not_active Expired - Lifetime

Patent Citations (8)

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