oxygenated gasoline composition and corrosion reduction method in an internal combustion engine

专利摘要:
COMPOSITION OF OXYGENED GASOLINE AND CORROSION REDUCTION METHOD IN AN INTERNAL COMBUSTION ENGINE. This invention relates to additive corrosion inhibiting combinations that offer long-acting performance in oxygenated gasoline mixtures comprising low carbon (3) or high carbon (greater than or equal to 4) alcohols or mixtures thereof and adapted for use in internal fuel and combustion engine delivery systems. The invention is also directed to a process for imparting anti-corrosion properties to oxygenates in gasoline fuel mixtures in which the oxygenate comprises biologically derived butanol.
公开号:BR112014015992B1
申请号:R112014015992-0
申请日:2012-12-28
公开日:2021-01-12
发明作者:Leslie R. Wolf；James J. Baustian
申请人:Butamax Advanced Biofuels Llc；
IPC主号:

专利说明:

[0001] [0001] This application claims the benefit of provisional application number 61 / 581,902, filed on December 30, 2011; the entire contents of which are incorporated by reference in this document. FIELD OF THE INVENTION
[0002] [0002] This invention relates to combinations of corrosion inhibitor that provide long-acting performance and mixtures of oxygenated gasolines comprising alcohols with a low carbon number (<3) or a high carbon number (greater than or equal to 4 ) or mixtures thereof and adapted for use in fuel delivery systems and internal combustion engines. The invention is also related to a process for imparting anti-corrosion properties to oxygenates in gasoline fuel mixtures. BACKGROUND OF THE INVENTION
[0003] [0003] Global concern over the growing shortage of supplies of crude oil has promoted the use of many materials as mixing agents in gasoline to extend the supply of fuel. The environmental concern also promoted the use of oxygenated gasoline in order to reduce emissions. Methanol, ethanol and t-butanol have emerged as the most widely used alcohol mixing agents. Methanol, often in mixtures with cosolvents, such as tert-butanol, has been used in commercial gasoline.
[0004] [0004] The use of polar oxygenates, such as methanol, ethanol, butanol, in gasoline mixtures, however, has far-reaching consequences. One of these consists of creating corrosion problems both in the logistics chain and in the vehicle itself. In pipes and storage tanks, rust, which can generally remain on the walls, is released by alcohol and transported through the system.
[0005] [0005] Perhaps, the biggest concerns with the use of commercial ethanol in gasoline mixtures are the phase separation problems that occur because alcohol containing water has limited solubility in gasoline. When phase separation occurs, corrosion of many of the metals and alloys that make up the vehicle's fuel distribution system and the vehicle's engine is promoted due to the water that comes in contact with the metals and metal alloys. Specifically, the fuel tank lead plate (steel coated with an 80-90% lead alloy and 10-20% tin), the zinc and aluminum cast fuel pump and carburetor parts and brass fittings , steel lines, etc. can corrode when exposed to gasoline-ethanol fuel mixtures.
[0006] [0006] In addition to bioethanol and ethyl tert-butyl ether, butanol or biobutanol biologically is increasingly considered as a substitute for bioethanol due to its advantages over bioethanol from the point of view of fuel preparation, that is, energy content higher, lower water miscibility, lower vapor pressure and lower corrosivity. The concentration of biobutanol in the fuel can reach up to 30% in v / v without the need to modify the engine. Since butanol fuel contains oxygen atoms, the stoichiometric air / fuel ratio is less than for gasoline and more fuel needs to be injected for the same amount of induced air. It has been found that the oxygen content improves combustion, therefore, lower CO and HC emissions can be expected. Biobutanol and its mixtures can be used directly in the current gasoline supply system, such as transport tanks and refueling infrastructure. Biobutanol can be mixed with gasoline without additional large-scale supply infrastructure, which is a great benefit as opposed to the use of bioethanol. Finally, biobutanol is non-toxic and non-corrosive and is easily biodegradable and does not pose a risk of soil and water pollution.
[0007] [0007] Compared to ethanol, biobutanol has important advantages when mixed with gasoline. The mixtures have better phase stability in the presence of water, low temperature properties, oxidation stability during long-term storage, distillation characteristics and volatility in relation to possible air pollution. Due to the fact that the oxygen content in biobutanol is lower than in ethanol, biobutanol can be added to gasoline in higher concentrations than the regulated limits for oxygen content in gasoline. The higher biobutanol content in gasoline does not require engine modification. The heating value (energy density) of biobutanol is close to that of gasoline, which has a positive effect on fuel consumption. Biobutanol has a slightly higher density when compared to gasoline, however, the increase in the density of biobutanol / gasoline mixtures is so small that it does not cause problems in meeting limits for automotive gasoline containing up to 30% in v / v of biobutanol.
[0008] [0008] This corrosion problem of oxygenated-containing gasoline can be remedied to some extent through the use of anhydrous or substantially anhydrous oxygenates as a mixing agent. However, if the fuel mixture is exposed to water, oxygenates, such as ethanol, will experience phase separation. Even in the absence of phase separation, corrosion can be caused by the presence of trace amounts of acetic acid, acetaldehyde, ethyl acetate and butanol in the fuel mixtures that are formed during the production of ethanol. Other corrosion problems can arise from dissolved mineral salts, such as highly corrosive sodium chloride, which can be captured by the fuel during production, storage and transport.
[0009] [0009] In the late 1980s, additive companies introduced special corrosion inhibiting additives for oxygenated gasolines. These additives are typically combinations of corrosion inhibitors of the carboxylic acid type used in conventional non-oxygenated gasoline and an amine neutralizer. Many of these materials are supposed to work by becoming adsorbed on the metal surface for which protection is desired. This adsorption results in the formation of a physical barrier that interferes with the transfer of corrosive reagents through the metal-solution interface. These additives have been used successfully in oxygenated gasoline containing ethanol or methanol plus co-solvents. However, the long-term effectiveness of corrosion inhibitors in oxygenated gasolines has not been well established.
[0010] [0010] The steel corrosion inhibitor test for gasoline is commonly performed with the NACE test. (National Association of Corrosion Engineers Method TM-01-72). However, due to OEM concerns about the stability of oxygenated gasoline mixtures, including the continued effectiveness of corrosion inhibitors, additive suppliers reported the heat aged performance in the NACE test and the Renewable Fuels Association (RFA) provided a guideline industry that recommends the NACE test after a prolonged period of environmental aging.
[0011] [0011] Thus, there is currently a need for a corrosion inhibitor that will contain or prevent corrosion from conventional systems that are used to store and transport commercial ethanol in gasoline fuel mixtures and one that will contain or prevent corrosion from vehicle fuel systems in which these fuels are primarily used. It is important that the corrosion inhibitor is effective in very small quantities to avoid any adverse effects, such as the addition of the fuel gum component, etc., as well as to minimize costs. The corrosion inhibitor must also not emulsify water.
[0012] [0012] OEM requirements are of particular concern for the effectiveness of the corrosion inhibitor over at least 120 days to emulate expected shelf life. After new automobiles, trucks and motor vehicles, in general, are assembled, their fuel tanks are usually loaded to some extent with an appropriate fuel before the vehicles are transported to their point of sale and delivery to the final consumer. Due to the global nature of the motor vehicle industry, with vehicle assembly often occurring in a different part of the world in relation to the vehicle's point of sale, the fuel that is placed in these fuel tanks often remains unused. for extended periods of time during transport and storage of vehicles.
[0013] [0013] During these periods of time, the fuel in the fuel tanks, which is now effectively in storage, must maintain its initial integrity and not degrade with the degradation that presents itself with subsequent starting and execution problems in the new vehicle and also by the formation of unwanted deposits in the fuel systems of vehicles leading to longer-term operability problems. The fuel used, then, must resist the formation of gum and sediment, minimize oxidation and prevent corrosion in the metal portions of the fuel system, as well as passivate new metal surfaces. Likewise, fuel storage facilities, for example, tanking, pumps and plumbing, at the motor vehicle assembly site are also susceptible to the deposition of these undesirable solid materials from the quantities of stored engine fuel awaiting transfer to newly assembled vehicles. .
[0014] [0014] The desired storage stability of the fuel is usually achieved by adding appropriate additives to the new fuel. Typically, complex combinations of antioxidants, such as aromatic diamines or hindered phenols, corrosion inhibitors based on carboxylic acid, and metal ion scavengers such as salicylidene diamines are added as a stability-inducing additive to the fuel.
[0015] [0015] Whether used alone or as part of an additive mixture of fuel stability, there is a need for corrosion inhibitors adapted for use in oxygenated gasolines that can maintain effectiveness over a long period of time.
[0016] [0016] Also, it has been found that the carboxylic acid functionality present in certain corrosion inhibitors has a detrimental effect on some additive formulations. Although the exact nature of these effects is difficult to determine, problems appear to arise when the acid corrosion inhibitor reacts with certain amine bases in additive formulations to form salts that precipitate out of solution to form an undesirable sludge. Not only is the present invention concerned with the identification of long acting corrosion inhibitors for oxygenated gasolines, it is desirable to limit the ratio of functionalities between acid and amine in order to minimize undesirable sludge.
[0017] [0017] Many corrosion inhibitors are known. For example, U.S. patent number 3,663,561 describes 2-hydrocarbylthio-5-mercapto-1,3,4-thiadiazoles defined as useful as sulfur scavengers.
[0018] [0018] US patent number 3,117,091 describes how rust prevention compounds for an oil-based carrier, such as engine gasoline, aviation gasoline, jet fuel, turbine oils, and the like, partial esters of an alkyl or succinic alkenyl produced by reacting a molar equivalent of a polyhydric alcohol with two molar equivalents of the anhydride.
[0019] [0019] US patent number 4,128,403 describes a fuel additive that has enhanced rust inhibiting properties comprising (1) 5 to 50 weight percent hydrocarbyl amine containing at least 1 hydrocarbyl group that has a molecular weight between about 300 and 5000, (2) from 0.1 to 10 weight percent of a C12 to C30 succinic acid or anhydride, (3) from 0.1 to 10 weight percent of a demulsifier, and (4) 40 to 90 weight percent of an inert hydrocarbon solvent.
[0020] [0020] US patent number 4,148,605 describes new esters of dicarboxylic acids that result from the condensation of alkenyl succinic anhydride with an aliphatic hydroxy acid that has from 2 to about 18 carbon atoms and amine salts of the acid ester as inhibitors of rust or corrosion in organic compositions.
[0021] [0021] US patent number 4,214,876 describes improved corrosion inhibitor compositions for hydrocarbon fuels consisting of mixtures of (a) about 75 to 95 weight percent of a polymerized unsaturated aliphatic monocarboxylic acid that has about from 16 to 18 carbons, and (b) about 5 to 25 weight percent of a monoalkenylsuccinic acid in which the alkenyl group has 8 to 18 carbons.
[0022] [0022] U.S. patent number 5,035,720 relates to a corrosion inhibiting composition comprising an oil-soluble adduct of a triazole and a basic nitrogen compound.
[0023] [0023] U.S. patent number 5,080,686 refers to the use of alkyl or alkenyl succinic acids to inhibit corrosion of metals in oxygenated fuel systems.
[0024] [0024] US 2008/0216393 refers to compositions and methods to reduce corrosion and improve the durability of combustion engines for a fuel containing ethanol and a corrosion inhibitor.
[0025] [0025] It may be desirable to have the long-acting corrosion inhibitor or mixtures thereof at low treatment rates, which can protect the fuel distribution infrastructure and internal combustion engines when exposed to a variety of oxygenated fuels that includes, specifically, gasoline mixtures that comprise biologically derived butanol, under different conditions, and that may not produce high levels of insoluble substances or cause the valve or injector to be attached to engines, however, comprise increased renewable content when compared to other gasoline mixtures oxygenated. BRIEF DESCRIPTION OF THE INVENTION
[0026] [0026] This invention relates to an oxygenated gasoline composition that has enhanced corrosion properties that comprise a gasoline mixture stock; about 1 to about 85% v / v of oxygenate or mixtures thereof, and an amount of one or more corrosion inhibitors in which the amount of corrosion inhibitor is from about 3.00 to about 50 ptb of the mixture of gasoline and the composition has an acid / amine eq / eq ratio ranging from about 1.00 to about 3.00. Oxygenate may include include butanol and, specifically, biologically derived butanol, isomers thereof, or mixtures of biological derived alcohols, such as biobutanol and bioethanol (bioethanol and biobutanol refer to biologically derived alcohols in which alcohols are produced by fermentation or other organic production).
[0027] [0027] This invention also relates to an oxygenated gasoline composition that has enhanced corrosion properties that comprise a gasoline mixture stock, about 1 to about 85% v / v oxygenate or mixtures thereof, and an amount of one or more corrosion inhibitors in which the amount of corrosion inhibitor is from about 1 to about 50 ptb of the gasoline mixture and in which said one or more corrosion inhibitors have an acid / amine equivalence ratio of about 1.00 to about 3.00.
[0028] [0028] In some embodiments, one or more corrosion inhibitors are selected from the group consisting of at least one dimer acid, at least one trimer acid, and mixtures thereof; said dimer and trimer acid resulting from dimerization or trimerization respectively of unsaturated fatty acids. In some embodiments, one or more corrosion inhibitors comprise at least one alkyl or alkenyl carboxylic acid. In some embodiments, said alkyl or alkenyl carboxylic acid is an alkenyl succinic acid.
[0029] [0029] In some embodiments, one or more corrosion inhibitors comprise at least one isoaliphatic acid that has a main saturated aliphatic chain that typically has about 6 to about 20 carbon atoms and at least one acyclic lower alkyl group.
[0030] [0030] In some embodiments, one or more corrosion inhibitors comprise at least one addition product of an unsaturated fatty acid with one or more unsaturated carboxylic reagents. In some embodiments, unsaturated fatty acid is selected from the group consisting of thalamic fatty acid and oleic acid.
[0031] [0031] In some embodiments, one or more corrosion inhibitors comprise at least one tricarboxylic acid. In some embodiments, tricarboxylic acid is a trimer acid, or one or more reaction products of an unsaturated fatty acid to an alpha, beta unsaturated dicarboxylic acid, or mixtures thereof. In some embodiments, tricarboxylic acid or its derivative is the reaction product of an alkenyl succinic anhydride and an alpha, unsaturated beta, or functional derivative thereof. In some embodiments, alpha dicarboxylic acid, beta unsaturated is selected from the group consisting of maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, and functional derivatives thereof.
[0032] [0032] In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of one or more olefins or polyalkenes with an alpha, beta unsaturated dicarboxylic acid. In some embodiments, one or more olefins are selected from the group consisting of 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1 -heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, and 1-tetracosene. In some embodiments, one or more olefins are selected from the group consisting of C15-18 alpha-olefins, C12 -C16 alpha-olefins, C14-16 alpha-olefins, C14-18 alpha-olefins, C16- alpha-olefins 18, C16-20 alpha-olefins, C18-24 alpha-olefins, and C22-28 alpha-olefins. In some embodiments, alpha dicarboxylic acid, beta unsaturated is selected from the group consisting of maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, and functional derivatives thereof. In some embodiments, the reaction product is dodecenyl succinic acid.
[0033] [0033] In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of at least one dimer acid with at least one amine. In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of at least one trimer acid with at least one amine. In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of at least one alkyl or alkenyl carboxylic acid with at least one amine. In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of at least one isoaliphatic acid that has a main saturated aliphatic chain that has from about 6 to about 20 carbon atoms and at least one lower alkyl group acyclic with at least one amine.
[0034] [0034] In some embodiments, one or more corrosion inhibitors comprise at least one addition product of an unsaturated fatty acid with one or more unsaturated carboxylic reagents, with at least one amine. In some embodiments, unsaturated fatty acid is selected from the group consisting of thalamic fatty acid and oleic acid.
[0035] [0035] In some embodiments, one or more corrosion inhibitors comprise at least one tricarboxylic acid and at least one amine. In some embodiments, tricarboxylic acid is a trimer acid, or one or more reaction products of an unsaturated fatty acid and an alpha, beta unsaturated dicarboxylic acid, or mixtures thereof. In some embodiments, the tricarboxylic acid or its derivative is one or more reaction products of an alkenyl succinic anhydride and an alpha, beta unsaturated dicarboxylic acid, or functional derivatives thereof. In some embodiments, alpha dicarboxylic acid, beta unsaturated is selected from the group consisting of maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, and functional derivatives thereof.
[0036] [0036] In some embodiments, the amine is a grease amine. In some embodiments, the grease amine is at least one selected from the group consisting of n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, stearylamine, oleamine, sebumilamine, cocoamine , and soybean amine.
[0037] [0037] In some embodiments, the amine is a primary amine ether. In some embodiments, the primary amine ether is represented by the formula, R1 (OR2) n -NH2, where R1 is a hydrocarbyl group of about 1 to about 20 carbon atoms, R2 is a divalent alkylene group that has about 2 to about 6 carbon atoms; and n is a number from one to about 10. In some embodiments, the primary amine ether is at least one selected from the group consisting of decyloxypropylamine, linear C-16 eteramine, and tridecyloxypropylamine, isohexyloxypropylamine, 2-ethylexyloxypropylamine, octyl / decyloxypropylamine, isodecyloxypropylamine, isododecyloxypropylamine, isotridecyloxypropylamine, and C12-15 alkyloxypropylamine.
[0038] [0038] In some embodiments, the amine is a primary tertiary alkyl amine represented by the formula (R1) 3C-NH2 where R1 are independent hydrocarbyl groups containing from 1 to about 24 carbon atoms, or the formula R1-C (R2) -NH2 where R1 is a hydrocarbyl group containing from 1 to about 24 carbon atoms and R2 is a divalent hydrocarbilene group, which contains from 1 to about 12 carbon atoms. In some embodiments, R2 is an alkylene group. In some embodiments, the amine is at least one selected from the group consisting of tert-butylamine, terchexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tercdodecylamine, tert-tetradecylamine, tert- hexadecylamine, tert-octadecylamine, tert-tetracos anilamine, and tert-octacosanilamine.
[0039] [0039] In some embodiments, the amine is represented by the formula R1-NH - (CH) n-NH2, where R1 is a hydrocarbyl group containing from 1 to about 24 carbon atoms and n is from 1 to about 20 .
[0040] [0040] In some embodiments, the amine is at least one selected from the group consisting of dicyclohexylamine and N, N-dimethylcyclohexylamine.
[0041] [0041] In some embodiments, the amine is a polyamine. In some embodiments, polyamine is a grease diamine. In some embodiments, the grease diamine is at least one selected from the group consisting of N-octyl diaminoalkanes, N-decyl diaminoalkanes, N-dodecyl diaminoalkanes, N-tetradecyl diaminoalkanes, N-hexadecyl diaminoalkanes, Noctadecyl diaminoalkanes, Noctadecyl diaminoalkanes diaminoalkanes, N-oleyl diaminoalkanes, N-tallow diaminoalkanes, N-cocoyl diaminoalkanes, and N-soy diaminoalkanes. In some embodiments, the grease diamine is at least one selected from the group consisting of N-coco-1,3-diaminopropane, N-soy-1,3-diaminopropane, N-tallow-1,3-diaminopropane, and N-oleyl-1,3-diaminopropane. In some embodiments, the polyamine is at least one selected from the group consisting of polyoxyalkylene diamine and polyoxyalkylene triamine. In some embodiments, the polyamine is at least one hydroxy-containing polyamine selected from the group consisting of N- (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, substituted mono (hydroxypropyl) -tetraethylene-pentamine, and N- (3-hydroxybutyl) tetramethylenediamine. In some embodiments, the polyamine is at least one alkylenopolyamine selected from the group consisting of methylenopolyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, piperazines and N- (amino alkyl) - substituted piperazines. In some embodiments, the alkylene polyamine is selected from the group consisting of ethylenediamine, triethylene tetramine, tris- (2-aminoethyl) amine, propylene diamine, trimethylenediamine, tripropylene tetramine, triethylene tetraamine, tetraethylenepentamine, hexaethylene and hexaethylene. In some embodiments, the polyamine is one or more polyhydric amines selected from the group consisting of diethanolamine, triethanolamine, tri- (hydroxypropyl) amine, tris- (hydroxymethyl) amino methane, 2-amino-2-methyl-1,3 - propanediol, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and N, N, N', N'- tetrakis (2-hydroxyethyl) ethylenediamine.
[0042] [0042] In some embodiments, the amine is at least one ether diamine represented by the formula NH2 (CH2) n-NH- (CH2) m-O-R, where n and m are independently 1 to about 10 and R is C1 – C18. In some embodiments, ether diamine is represented by the formula ROCH2CH2CH2NHCH2CH2CH2NH2 where R is C3 – C18. In some embodiments, ether diamine is selected from the group consisting of isodecyloxypropyl-1,3-diaminopropane, isododecyloxypropyl-1,3-diaminopropane, and isotridecyloxypropyl-1,3-diaminopropane.
[0043] [0043] In some embodiments, one or more corrosion inhibitors comprise the grease amine. In some embodiments, the grease amine is at least one selected from the group consisting of n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, stearylamine, oleamine, sebumilamine, cocoamine , and soybean amine.
[0044] [0044] In some embodiments, one or more corrosion inhibitors comprise a primary amine ether. In some embodiments, the primary amine ether is represented by the formula R1 (OR2) n -NH2, where R1 is a hydrocarbyl group of about 1 to about 20 carbon atoms, R2 is a divalent alkylene group that has about 2 about 6 carbon atoms; and n is a number from one to about 10. In some embodiments, the primary amine ether is at least one selected from the group consisting of decyloxypropylamine, linear C-16 eteramine, and tridecyloxypropylamine, isohexyloxypropylamine, 2-ethylexyloxypropylamine, octyl / decyloxypropylamine, isodecyloxypropylamine, isododecyloxypropylamine, isotridecyloxypropylamine, and C12-15 alkyloxypropylamine.
[0045] [0045] In some embodiments, one or more corrosion inhibitors comprise a tertiary alkyl primary amine represented by the formula (R1) 3C-NH2 where R1 are independent hydrocarbyl groups containing from 1 to about 24 carbon atoms, or formula R1-C (R2) -NH2 wherein R1 is a hydrocarbyl group containing from 1 to about 24 carbon atoms and R2 is a divalent hydrocarbilene group, containing from 1 to about 12 carbon atoms. In some embodiments, R2 is an alkylene group. In some embodiments, the primary tertiary alkyl amine is at least one selected from the group consisting of tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tert- dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracos anilamine, and tert-octacosanilamine.
[0046] [0046] In some embodiments, one or more corrosion inhibitors comprise at least one amine represented by the formula R1- NH - (CH) n-NH2, where R1 is a hydrocarbyl group containing from 1 to about 24 carbon atoms and n is from 1 to about 20.
[0047] [0047] In some embodiments, one or more corrosion inhibitors comprise at least one polyamine. In some embodiments, polyamine is a grease diamine. In some embodiments, grease diamine is at least one selected from the group consisting of N-octyl diaminoalkanes, N-decyl diaminoalkanes, N-dodecyl diaminoalkanes, Ntetradecyl diaminoalkanes, N-hexadecyl diaminoalkanes, N-octadecyl diaminoalkanes, N-octadecyl diaminoalkanes diaminoalkanes, N-oleyl diaminoalkanes, N-tallow diaminoalkanes, N-cocoyl diaminoalkanes, and N-soy diaminoalkanes. In some embodiments, the grease diamine is at least one selected from the group consisting of N-coco-1,3-diaminopropane, N-soy-1,3-diaminopropane, N-tallow-1,3-diaminopropane, and N-oleyl-1,3-diaminopropane. In some embodiments, the polyamine is at least one selected from the group consisting of polyoxyalkylene diamine and polyoxyalkylene triamine. In some embodiments, the polyamine is at least one hydroxy-containing polyamine selected from the group consisting of N- (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, substituted mono (hydroxypropyl) -tetraethylene-pentamine, and N- (3-hydroxybutyl) tetramethylenediamine. In some embodiments, the polyamine is at least one alkylene polyamine selected from the group consisting of methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, piperazines and N-amino alkylpiperazines. In some embodiments, an alkylene polyamine is selected from the group consisting of ethylenediamine, triethylene tetramine, tris- (2-aminoethyl) amine, propylene diamine, trimethylenediamine, tripropylene tetramine, triethylene tetraamine, tetraethylenepentamine, hexaethylene and hexaethylene. In some embodiments, the polyamine is at least one polyhydric amine selected from the group consisting of diethanolamine, triethanolamine, tri- (hydroxypropyl) amine, tris- (hydroxymethyl) amino methane, 2-amino-2-methyl-1,3 - propanediol, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and N, N, N', N'- tetrakis (2-hydroxyethyl) ethylenediamine.
[0048] [0048] In some embodiments, one or more corrosion inhibitors comprise at least one ether diamine represented by the formula NH2 (CH2) n-NH- (CH2) mOR, where neither are independently 1 to about 10 and R is C1 – C18 . In some embodiments, ether diamine is represented by the formula ROCH2CH2CH2NHCH2CH2CH2NH2 where R is C3 - C18. In some embodiments, the diamine ether is selected from the group consisting of isodecyloxypropyl-1,3-diaminopropane, isododecyloxypropyl-1,3-diaminopropane, and isotridecyloxypropyl-1,3-diaminopropane.
[0049] [0049] In some embodiments, one or more corrosion inhibitors comprise at least one amide formed by the reaction of unsaturated fatty acid and N-methyl glycine. In some embodiments, the amide is N-methylN- (1-oxo-9-octadecenyl) glycine.
[0050] [0050] In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of linoleic acid or tall oil fatty acid with acrylic acid. In some embodiments, the reaction product is 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, or 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid.
[0051] [0051] In some embodiments, one or more corrosion inhibitors comprise at least one reaction product of unsaturated fatty acid and N- (2-hydroxyethyl) -1,2-diaminoethane. In some embodiments, the reaction product is 1- (2-hydroxyethyl) -2- (8-heptadecenyl) -2-imidazoline.
[0052] [0052] In some embodiments, the fatty acid is present as a by-product of the processing of the raw material for the production of the biologically derived oxygenate. In some embodiments, the fatty acid is present as an extractor to recover the biologically derived oxygenate from a fermentation broth. In some embodiments, the oxygenate is isobutanol. In some embodiments, the fatty acid is derived from corn oil. In some embodiments, the extractor is fatty acid or corn oil oleic acid.
[0053] [0053] In some embodiments, the composition of oxygenated gasoline comprises two or more, three or more, or four or more corrosion inhibitors.
[0054] [0054] In some embodiments, at least one oxygenate or mixture thereof is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ketones, esters and mixtures thereof. In some embodiments, the composition comprises an amount equal to or less than about 5% in v / v of methanol. In some embodiments, the composition comprises an amount equal to or less than about 10% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 20% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 30% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 10% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 20% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 30% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 40% v / v of butanol. In some embodiments, the composition comprises about 16% v / v isobutanol. In some embodiments, the composition comprises about 24% v / v isobutanol. In some embodiments, the composition comprises about 5-65% v / v by volume of ethanol and about 5 to 50% v / v of butanol. In some embodiments, said oxygenate comprises at least about 5% renewable component. In some embodiments, said renewable component comprises biologically derived ethanol, biologically derived butanol or mixtures thereof. In some embodiments, the oxygenated gasoline composition further comprises one or more deposit control additives.
[0055] [0055] This invention also relates to an additive concentrate suitable for mixing with oxygenated gasoline which comprises about 1 to about 85% v / v oxygenate or mixtures thereof, to provide protection against corrosion in internal combustion engines and fuel infrastructure systems, in which the additive concentrate comprises a solvent and from 10% by weight to 50% by weight based on the solvent of at least one corrosion inhibitor. In some embodiments, the solvent is an organic solvent, base stock of lubricating oil or mixture thereof.
[0056] [0056] Another embodiment of the invention relates to a method for reducing corrosion in an internal combustion engine and fuel infrastructure systems that comprises operating the internal combustion engine or the fuel infrastructure system with a fuel composition that comprises a gasoline mixture stock, about 1 to about 85% v / v oxygenate, and at least one corrosion inhibitor where the concentration of the total corrosion inhibitor is from about 3.00 to about 50 ptb and the composition has an acid / amine eq / eq ratio ranging from about 1.00 to about 3.00.
[0057] [0057] Another aspect of the invention provides a method for reducing corrosion in an internal combustion engine and fuel infrastructure systems which comprises operating the internal combustion engine or the fuel infrastructure system with a fuel composition comprising a stock of fuel mixture, about 1 to about 85% v / v oxygenate, and one or more corrosion inhibitors in an amount of about 1.0 to about 50 ptb and in which said one or more inhibitors of corrosion have an acid / amine equivalence ratio of about 0.1 to about 3.
[0058] [0058] Another aspect of the invention provides oxygenated gasoline for use in internal combustion engines that comprise a gasoline mixture stock, about 1 to about 85% v / v of oxygenate or mixtures thereof, and at least two corrosion inhibitors where the concentration of the total corrosion inhibitor is about 3.00 to about 50 ptb of the gasoline mixture and the composition has an acid / amine eq / eq ratio ranging from about 1.00 to about 3.00.
[0059] [0059] Yet another aspect of the invention is to provide a method for imparting corrosion inhibiting properties to oxygenated gasoline mixtures comprising a gasoline mixture stock and about 1 to about 85% v / v oxygenate or mixtures thereof ; said method which comprises mixing said gasoline and oxygenate with at least two corrosion inhibitors, wherein the concentration of the total corrosion inhibitor is from about 3.00 to about 50 ptb and the composition has a ratio of eq / acid / amine eq ranging from about 1.00 to about 3.00.
[0060] [0060] Another aspect of the invention consists of a method for producing the corrosion-inhibited oxygenated gasoline composition comprising the addition of at least one corrosion inhibitor to an oxygenate-gasoline mixture stock. In some embodiments, the oxygenated - gasoline mixture stock comprises methanol, ethanol, butanol, or mixtures of these. In some embodiments, butanol is mixed with one or more gasoline mixture stocks and, optionally with one or more suitable oxygenates. In some embodiments, one or more mixtures of gasoline, butanol, and optionally one or more suitable oxygenates can be mixed in any order. In some embodiments, one or more suitable oxygenates and a butanol isomer can be added at several different locations or in multiple stages. In some embodiments, one or more butanols and optionally one or more suitable oxygenates can be added at any point along the distribution chain. In some embodiments, one or more gasoline mixture stocks, one or more isomers of butanol and, optionally, one or more suitable oxygenates can be combined in a refinery. In some embodiments, other components or additives can also be added to the gasoline composition at a refinery, terminal, retail location, or any other suitable point in the distribution chain.
[0061] [0061] Yet another aspect of the invention is to provide a method for improving the storage stability of an oxygenated fuel composition which comprises adding to a fuel mixture stock that has from about 1 to about 85% in v / v oxygenate, one or more deposit control additives and one or more corrosion inhibitors in an amount of about 3.00 to about 50 ptb and wherein said one or more corrosion inhibitors have an acid equivalence ratio / amine from about 1.00 to about 3.00.
[0062] [0062] Yet another aspect of the invention is to provide a method for improving the storage stability of an oxygenated fuel composition which comprises adding to a fuel mixture stock that has from about 1 to about 85% in v / v oxygenate, one or more deposit control additives and one or more corrosion inhibitors in an amount of about 1.0 to about 50 ptb and wherein said one or more corrosion inhibitors have an acid equivalence ratio / amine from about 0.1 to about 3. In some embodiments, corrosion protection and storage stability of the oxygenated gasoline composition is maintained for at least 12 weeks.
[0063] [0063] Another aspect of the invention consists of a storage-stable isobutanol composition comprising isobutanol and one or more corrosion inhibitors.
[0064] [0064] Yet another aspect of the invention is to provide an oxygenated gasoline composition that has enhanced corrosion properties that comprise a gasoline mixture stock, about 1 to about 85% v / v oxygenate or mixtures thereof, and an amount of one or more corrosion inhibitors where said amount is from about 0.5 ptb to about 5 ptb and where one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 10 to about 1: 0. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 9. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 0.
[0065] [0065] In some embodiments, one or more corrosion inhibitors have a nitrogen content less than about 100 ppm. In some embodiments, one or more corrosion inhibitors have a nitrogen content of less than about 70 ppm. In some embodiments, one or more corrosion inhibitors have a nitrogen content of less than about 50 ppm. In some embodiments, one or more corrosion inhibitors have no detectable amines.
[0066] [0066] In some embodiments, one or more corrosion inhibitors comprise at least one alkyl or alkenyl carboxylic acid. In some embodiments, said alkenyl carboxylic acid is tetrapopenylsuccinic acid. In some embodiments, one or more corrosion inhibitors comprise from about 25 to about 75% w / w of said alkyl or alkenyl carboxylic acid. In some embodiments, one or more corrosion inhibitors comprise from about 30 to about 70% w / w of said alkyl or alkenyl carboxylic acid. In some embodiments, one or more corrosion inhibitors comprise from about 30 to about 60% w / w of tetrapopenylsuccinic acid. In some embodiments, one or more corrosion inhibitors comprise from about 60 to about 70% w / w of a carboxylic acid ester or functional derivative thereof. In some embodiments, one or more corrosion inhibitors further comprise a solvent that comprises xylenes and ethyl benzene. In some embodiments, one or more corrosion inhibitors comprise from about 1 to about 15% w / w of said alkyl or alkenyl carboxylic acid. In some embodiments, one or more corrosion inhibitors comprise from about 5 to about 10% w / w of said alkyl or alkenyl carboxylic acid. In some embodiments, one or more corrosion inhibitors additionally comprise about 50 to about 100% w / w of at least one amine. In some embodiments, one or more corrosion inhibitors additionally comprise about 60 to about 100% w / w of at least one alkyl amine.
[0067] [0067] In some embodiments, the said amount of one or more corrosion inhibitors is from about 1 ptb to about 4 ptb. In some embodiments, said amount of one or more corrosion inhibitors is from about 1 ptb to about 2 ptb. In some embodiments, said amount of one or more corrosion inhibitors is about 1.6 ptb. In some embodiments, said amount of one or more corrosion inhibitors is from about 3 ptb to about 5 ptb. In some embodiments, the said amount of one or more corrosion inhibitors is about 4 ptb.
[0068] [0068] In some embodiments, at least one oxygenate or mixture thereof is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ketones, esters and mixtures thereof. In some embodiments, the composition comprises an amount equal to or less than about 5% in v / v methanol. In some embodiments, the composition comprises an amount equal to or less than about 10% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 20% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 30% in v / v of ethanol. In some embodiments, the composition comprises an amount equal to or less than about 10% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 20% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 30% in v / v of butanol. In some embodiments, the composition comprises an amount equal to or less than about 40% v / v of butanol. In some embodiments, the composition comprises about 16% v / v isobutanol. In some embodiments, the composition comprises about 24% v / v isobutanol. In some embodiments, the composition comprises about 5-65% v / v by volume of ethanol and about 5 to 50% v / v of butanol.
[0069] [0069] Another aspect of the invention is to provide a method for reducing corrosion in an internal combustion engine and fuel infrastructure systems that comprises operating the internal combustion engine or the fuel infrastructure system with a fuel composition that comprises a stock of fuel mixture, about 1 to about 85% v / v of oxygenate or mixtures thereof, and an amount of one or more corrosion inhibitors where said amount is about 0.5 ptb at about 5 ptb and where one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1:10 to about 1: 0.
[0070] [0070] Yet another aspect of the invention is to provide a method for producing the corrosion-inhibited oxygenated gasoline composition comprising the addition of at least one corrosion inhibitor to an oxygenate-gasoline mixture stock.
[0071] [0071] Another aspect of the invention is to provide a method for improving the storage stability of an oxygenated fuel composition which comprises adding to a fuel mixture stock that has from about 1 to about 85% v / v of oxygenated, one or more deposit control additives and one or more corrosion inhibitors in an amount of about 0.5 to about 5 ptb and in which one or more corrosion inhibitors have an acid equivalence ratio: amine of about 1:10 to about 1: 0. In some embodiments, the storage stability and corrosion protection of the oxygenated fuel composition is maintained for at least 12 weeks.
[0072] [0072] Yet another aspect of the invention is to provide a storage-stable isobutanol composition comprising oxygenated gasoline composition in which the oxygenated is isobutanol.
[0073] [0073] Another aspect of the invention is to provide a corrosion inhibited oxygenate comprising about 90 to about 100% w / w of an alcohol and about 10 to about 200 ptb of a corrosion inhibitor, wherein the inhibitor of corrosion has an acid: amine equivalence ratio of about 1:10 to about 1: 0. In some embodiments, alcohol is biologically derived. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof.
[0074] [0074] Yet another aspect of the invention is to provide a method for producing oxygenated gasoline which comprises mixing the corrosion inhibited oxygenate with the base gasoline stock to produce oxygenated gasoline. In some embodiments, the corrosion-inhibited oxygenate comprises an alcohol that is biologically derived. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof.
[0075] [0075] In some embodiments, the invention provides an oxygenated gasoline composition comprising one or more corrosion inhibitors and about 1 to about 30% in v / v of a biologically derived alcohol. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof. In some embodiments, the concentration of the corrosion inhibitor is from about 0.5 ptb to about 5 ptb. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 0.1 to about 3. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio about 1:10 to about 1: 0.
[0076] [0076] It should be understood that both the general description and the detailed description below are exemplary and explanatory only and are intended to provide additional explanation of the present description, as claimed. DETAILED DESCRIPTION OF THE INVENTION
[0077] [0077] The corrosion inhibitors of oxygenated gasoline of the present invention are intended for use in fuels (mainly automotive fuels) containing up to 85 percent by volume of oxygen, preferably from about 2 to about 50 percent by volume and , more preferably, from about 5 to about 30 percent by volume of at least one alcohol. The alcohol may be one or a mixture of methanol, ethanol, propyl or butanol and is preferably isobutanol. Where alcohol is isobutanol, the percentage by volume of oxygenate can be 2, 4, 5, 6, 8, 10, 11, 12, 16, 20, 24 (and any integers between) percent by volume. The oxygenated gasolines of the present invention are intended for use as a spark ignition engine.
[0078] [0078] Except where otherwise defined, all technical and scientific terms used in this document have the same meaning as commonly understood by an element versed in the technique to which this invention belongs. In the event of a conflict, this order including definitions will have control. Also, except where otherwise required by context, singular terms must include the plural and plural terms must include the singular. All publications, patents and other references mentioned in this document are incorporated by reference in their entirety for all purposes.
[0079] [0079] In order to further define that invention, the following terms and definitions are provided in this document.
[0080] [0080] As used in this document, the terms "comprises", "which comprises", "includes", "which includes", "has", "has", "contains" or "contains", or any other variation of these, will be understood to imply the inclusion of an established whole number or group of whole numbers, however, not the exclusion of any other whole number or group of whole numbers, for example, a composition, a mixture, a process, a method , an article or device comprising a list of elements is not necessarily limited to those elements only, but may include other elements not expressly listed or inherent in such a composition, mixture, process, method, article or device. expressly stated to the contrary, "or" refers to one or even and not to one or exclusive. For example, a condition A or B is satisfied by any of the following instructions: A is true (or present) and B is false (or not present), A is false (or does not and B is true (or present), and both A and B are true (or present).
[0081] [0081] As used herein, the term "consists of”, or variations, such as, "consist of" or "which consists of", as used throughout the specification and claims, indicates the inclusion of any number integer or group of integers cited, however, that no additional integer or group of integers can be added to the specified method, structure or composition.
[0082] [0082] As used herein, the term "consists essentially of”, or variations, such as, "consists essentially of" or "consisting essentially of", as used throughout the specification and the claims, indicates the inclusion of any integer or group of integers cited, and the optional inclusion of any integer or group of integers cited that does not materially alter the basic or new properties of the specified method, structure or composition.
[0083] [0083] Also, the indefinite article "one" that precedes an element or component of the invention is intended to be non-restrictive in relation to the number of instances, that is, occurrences of the element or component. Therefore "one" must be read to include or at least one, and the word form in the singular of the element or component also includes the plural, except where the number is obviously intended to be singular.
[0084] [0084] The term "invention" or "present invention", as used herein, is not a non-limiting term and is not intended to refer to a single embodiment of the particular invention, however, it encompasses all possible embodiments, as described in the application.
[0085] [0085] As used in this document, the term "about" which modifies the amount of an ingredient or reagent of the invention employed refers to the variation in the numerical amount that can occur, for example, through typical measurement and handling procedures. liquids used to produce concentrates or solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source or purity of the ingredients used to produce the compositions or perform the methods; and the like. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial blend. Whether or not modified by the term "about", the claims include equivalents for the quantities. In one embodiment, the term "about" means within 10% of the reported numerical value; in another embodiment, within 5% of the reported numerical value.
[0086] [0086] The term "alcohol", as used in this document, refers to any one of a series of hydroxyl compounds, the simplest of which are derived from saturated hydrocarbons, which have the general formula CnH2n + 1OH. Examples of alcohol include methanol, ethanol and butanol.
[0087] [0087] "Butanol", as used herein, refers specifically to the butanol isomers 1-butanol (1-BuOH), 2-butanol (2-BuOH), tert-butanol (t-BuOH), and / or isobutanol (iBuOH or i-BuOH or I-BUOH, also known as 2-methyl-1-propanol), individually or as mixtures thereof. Occasionally, when referring to butanol esters, the terms "butyl esters" and "butanol esters" can be used interchangeably. Butanol can be biologically derived (ie, biobutanol), for example. Biologically derived and biologically originated are used interchangeably to refer to fermentative (or some other biological) production. See, for example, U.S. patent number 7,851,188, not incorporated herein by reference in its entirety.
[0088] [0088] The term "renewable component", as used in this document, refers to a component that is not derived from petroleum or petroleum products.
[0089] [0089] The term "fuel", as used in this document, refers to any material that can be used to generate energy to produce mechanical work in a controlled manner. Examples of fuels include, but are not limited to, biofuels (ie fuels that are somehow derived from biomass), gasoline, gasoline, diesel and airplane fuel. It is understood that the specific components and subsidies for suitable fuels may vary according to seasonal and regional guidelines.
[0090] [0090] The term "fuel mixture" or "mixed fuel", as used in this document, refers to a mixture containing at least one fuel and one or more alcohols.
[0091] [0091] The term "gasoline", as used in this document, generally refers to a volatile mixture of liquid hydrocarbons that may optionally contain small amounts of additives. This term includes, but is not limited to, conventional gasoline, oxygenated gasoline, reformulated gasoline, biogasoline (that is, gasoline that is somehow biologically derived from biomass), and Fischer-Tropsch gasoline, and mixtures thereof. In addition, the term "gasoline" includes a mixture of gasoline, gasoline mixtures, mixed gasoline, a gasoline mixture stock, gasoline mixture stocks, and mixtures thereof. It is understood that the specific components and subsidies for suitable fuels may vary according to seasonal and regional guidelines. For example, gasoline standards for sale in much of the United States are generally established by the ASTM D 4814 Standard Specification number ("ASTM D 4814") which is incorporated by reference into this document. Gasoline standards for sale in much of Europe are generally established by the European standard EN228: 2008, which is also incorporated by reference in this document. Additional federal and state regulations supplement this ASTM standard. The gasoline specifications set out in ASTM D 4814 vary according to numerous parameters that affect volatility and combustion, such as climate, season, geographic location and altitude.
[0092] [0092] The terms "gasoline mixture" and "mixed gasoline", as used in this document, refer to a mixture containing at least one gasoline and / or sub-grade of gasoline and / or mixtures of one or more mixture components refinery gasoline (for example, alkylate, reformate, FCC naphtha, etc.) and, optionally, one or more alcohols. A mixture of gasoline includes, but is not limited to, unleaded gasoline suitable for combustion in an automotive engine.
[0093] [0093] The terms "American Society for Tests and Materials" and "ASTM", as used in this document, refer to the international standardization organization that develops and publishes voluntary consensus technical standards for a wide range of materials, products, systems , and services, including fuels.
[0094] [0094] The term "corrosion", as used herein, refers to any degradation, rust, weakening, deterioration, softening, and the like, of any surface, including engine surfaces or an engine part or component or a engine component or part due to exposure to, or combustion of, an oxygenated fuel.
[0095] [0095] The term "corrosion inhibition" or "corrosion reduction", as used in this document, refers to any improvement in minimizing, reducing, eliminating or preventing corrosion.
[0096] [0096] The corrosion inhibitors of the present invention comprise low molecular weight (i.e., <700) amines (mono, di, tri, and poly), amines, etherins, imines, imidazolines, thiadiazoles, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and esters and functional derivatives of mono-, di-, and tricarboxylic acids, dimers, trimers, pphenylenediamine, N, N-dimethylcyclohexylamine and dicyclohexylamine, succinic anhydrides substituted with alkyl and acids and mixtures of these and salts thereof.
[0097] [0097] Corrosion inhibitors useful herein may also include or comprise tetrapopenylsuccinic acid or anhydride and polymers thereof, and dodecenyl succinic acid (DDSA) or anhydride and polymers thereof.
[0098] [0098] In some embodiments of the invention, one or more corrosion inhibitors comprise from about 1 to about 85% w / w, about 3 to about 85% w / w, about 5 to about 85% w / w, about 1 to about 15% w / w, about 3 to about 13% w / w, about 5 to about 10% w / w, about 6 to about 9% w / w , about 15 to about 85% w / w, about 25 to about 75% w / w, about 30 to about 70% w / w, about 30 to about 60% w / w, or about 60 to about 70% w / w of an alkyl or alkenyl carboxylic acid, or ester or functional derivative thereof. In some embodiments, one or more corrosion inhibitors comprise from about 30 to about 60% w / w of tetrapopenylsuccinic acid. In some embodiments, one or more corrosion inhibitors comprise from about 60 to about 70% w / w of a carboxylic acid ester or functional derivative thereof.
[0099] [0099] BioTEC® 9881 (listed as Tec 9881 in Table 1) is an example of a commercially available corrosion inhibitor according to the invention, which is believed to contain about 60 to about 100% w / w alkyl amine , and about 5 to about 10% w / w of a long chain carboxylic acid. BioTEC® 9881 is believed to have an acid: amine equivalence ratio of about 1: 9, with a nitrogen content of about 6.9%. BioTEC 9880 (listed as Tec 9880 in Table 1) is an example of a commercially available corrosion inhibitor according to the invention, which is believed to contain 30 to about 60% w / w tetrapopenylsuccinic acid. BioTEC® 9880 is believed to have an acid: amine equivalence ratio of about 1: 0, with a nitrogen content of less than about 0.1%. Lubrizol 541 (listed as Lubrizol LZ 541 in Table 1) is an example of a commercially available corrosion inhibitor according to the invention, which is believed to contain about 60 to about 70% w / w of an acid ester carboxylic or functional derivative thereof. Lubrizol® 541 is believed to have an acid: amine equivalence ratio of about 1: 0, with a nitrogen content of less than about 0.1%.
[0100] [0100] In one embodiment, the corrosion inhibitor is the product of the combination of an organic acid or dimer acid or trimer acid and an amine, diamine, or polyamine.
[0101] [0101] In one embodiment, the corrosion inhibitor is the product of combining an organic acid or dimer acid or trimer acid with a grease amine. Fatty amines are those that contain about 8 to about 30, or about 12 to about 24 carbon atoms. Fatty amines include n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, stearylamine, oleamine, seboylamine, cocoamine, soy amine, etc. Also, useful fatty amines include commercially available fatty amines, such as "Armeen" amines (products available from Akzo Chemicals, Chicago, Ill.), Such as Akzo's Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, where the letter designation refers to the fatty group, such as cocoa, oleyl, tallow or stearyl groups.
[0102] [0102] Other useful amines include ether primary amines, such as those represented by the formula, R1 (OR2) n -NH2, where R1 is a hydrocarbyl group of about 1 to about 20, or 5 to about 18 carbon atoms, R2 is a divalent alkylene group that has about 2 to about 6 carbon atoms; and n is a number from one to about 10, or from about one to about five, or one. An example of an amine ether is available under the name SURFAM® amines produced and marketed by Mars Chemical Company, Atlanta, Ga. The etherins include those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C16), SURFAM P17B (tridecyloxypropylamine) isohexyloxypropylamine, 2-ethylexyloxypropylamine, octyl / decyloxypropylamine, isodecyloxypropylamine, isodyloxypropylamine, iso.
[0103] [0103] Still other useful amines include ether diamines represented by the formula NH2 (CH2) n-NH- (CH2) m-O-R, where n and m are independently 1 to about 10 and R is C1 – C18. The preferred diamine ether is that of the formula ROCH2CH2CH2NHCH2CH2CH2NH2 where R is C3-C18, preferably C6 to C15 and include as examples isodecyloxypropyl-1,3-diaminopropane, isododecyloxypropyl-1,3-diaminopropane, isotridecyloxypropyl,3.
[0104] [0104] The term “hydrocarbyl”, as used in this document, means that the group in question is mainly composed of hydrogen and carbon atoms and is linked to the rest of the molecule through a carbon atom, however, it does not exclude the presence of other atoms or groups in an insufficient proportion to substantially impair the hydrocarbon characteristics of the group. The hydrocarbyl group is preferably composed only of hydrogen and carbon atoms. Advantageously, the hydrocarbyl group is an aliphatic group, preferably an alkyl or alkylene group, especially alkyl groups, which can be linear or branched.
[0105] [0105] In another embodiment, the corrosion inhibitor is the product of combining an organic acid or dimer acid or trimer acid with a tertiary aliphatic primary amine. Generally, the aliphatic group, and in one embodiment, an alkyl group, contains from about 4 to about 30, or from about 6 to about 24, or from about 8 to about 22 carbon atoms. Generally, primary tertiary alkyl amines are monoamines represented by the formula (R1) 3C-NH2 where R1 are independent hydrocarbyl groups containing from 1 to about 24 carbon atoms, or a formula R1-C (R2) -NH2 in that R1 is a hydrocarbyl group containing from 1 to about 24 carbon atoms and R2 is a divalent hydrocarbene group, preferably an alkylene group, containing from 1 to about 12 carbon atoms. Such amines are illustrated by tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tertetracosanilamine, and tert-octacosanilamine.
[0106] [0106] In another embodiment, the corrosion inhibitor is the product of the combination of an organic acid or dimer acid or trimer acid with an amine represented by the formula R1-NH - (CH) n-NH2, where R1 is a hydrocarbyl group which contains from 1 to about 24 carbon atoms and n is from 1 to about 20.
[0107] [0107] Amine mixtures are also useful for the purposes of this invention. Illustrative amine mixtures of this type are "Primene 81R" which is a mixture of C11-C14 tertiary alkyl primary amines and "Primene JM-T" which is a mixture of C18-C22 tertiary alkyl primary amines (both available from Dow Chemical Company). Primary tertiary alkyl amines and methods for their preparation are known to those skilled in the art. The primary tertiary alkyl amine useful for the purposes of this invention and the methods for its preparation are described in U.S. Patent No. 2,945,749, which is incorporated herein by reference for its teaching in this regard.
[0108] [0108] In another embodiment, the corrosion inhibitor is a basic acylated amine. The basic acylated amine includes reaction products of one or more carboxylic acylating agents and one or more amines, preferably a polyamine. Basic acylated amines are prepared by reacting an excess of amine with the carboxylic acylating agent. In one embodiment, more than one equivalent of amine is reacted with each equivalent of the acylating agent's carboxylic group. Amine equivalents are based on the number of nitrogen atoms in the amine. The equivalent weight of the carboxylic acylating agent is based on the number of carboxylic groups (for example, COO), such as acids, lower esters, etc. in each acylating agent. In one embodiment, at least about 1.2, preferably at least about 1.4 equivalents of amine are reacted with each equivalent of the carboxylic group of the acylating agent. Typically, up to about 8 or, preferably, up to about 6, or more preferably, up to about 4 equivalents of amine are reacted with each equivalent of the carboxylic group of the acylating agent.
[0109] [0109] In one embodiment, the carboxylic acylating agent is present in situ as a by-product of the raw material used to produce a biologically derived oxygenated component or an extractor by-product used to extract the biologically derived oxygenate from a fermentation broth.
[0110] [0110] In another embodiment, the corrosion inhibitor comprises at least one ether diamine represented by the formula NH2 (CH2) n-NH- (CH2) m-O-R, where n and m are independently 1 to about 10 and R is C1 – C18. The preferred diamine ether is that of the formula ROCH2CH2CH2NHCH2CH2CH2NH2 where R is C3-C18, preferably C6 to C15 and includes isodecyloxypropyl-1,3-diaminopropane, isododecyloxypropyl-1,3-diaminopropane, isotridecyloxypropyl-1,3-diaminopropane.
[0111] [0111] Basic acylated amines are prepared from one or more amines and one or more carboxylic acylating agents. Carboxylic acylating agents include fatty acids, isoaliphatic acids, dimer acids, addition dicarboxylic acids, trimer acids, addition tricarboxylic acids, and hydrocarbyl substituted caryl acyl agents. In one embodiment, the carboxylic acylating agent is one of the unsaturated fatty acids described above. Fatty acids can also be the saturated analogues of unsaturated fatty acids.
[0112] [0112] In another embodiment, the corrosion inhibitor of the present invention comprises isoaliphatic acids. Such acids contain a saturated main aliphatic chain, which typically has from about 6 to about 20 carbon atoms and at least one, but generally less than or equal to about four, lower acyclic lower alkyl groups. Specific examples of such isoaliphatic acids include 10-methyl-tetradecanoic acid, 3-ethyl-hexadecanoic acid, and 8-methyl-octadecanoic acid. Isoaliphatic acids include branched-chain acids prepared by oligomerization of commercial fatty acids, such as oleic, linoleic and tall oil fatty acids.
[0113] [0113] In another embodiment, the corrosion inhibitor of the present invention comprises dimer acids. Dimer acids include products that result from dimerization of unsaturated fatty acids and generally contain an average of about 18 to about 44, or about 28 to about 40 carbon atoms. Dimer acids are described in U.S. patent numbers 2,482,760. 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468, 3,157,681, and 3,256,304, all descriptions of which are incorporated herein by way of reference.
[0114] [0114] In another embodiment, the corrosion inhibitor of the present invention comprises addition carboxylic acids, which are addition products (4 + 2 and 2 + 2) of an unsaturated fatty acid, such as talanol and oleic acids, with one or more unsaturated carboxylic reagents. These acids are taught in U.S. Patent No. 2,444,328, the description of which is incorporated herein by reference.
[0115] [0115] In one embodiment, unsaturated fatty acid is present in situ as a by-product of the raw material used to produce a biologically derived oxygenated component or a by-product of extractors used to extract the biologically derived oxygenate from a fermentation broth.
[0116] [0116] In another embodiment, the corrosion inhibitor of the present invention comprises tricarboxylic acids. Examples of tricarboxylic acids include trimer acids and the reaction product of an unsaturated carboxylic acid (such as unsaturated fatty acids) and an alpha, beta unsaturated dicarboxylic acid (such as maleic, itaconic, and citraconic acylating agents, preferably , maleic acid). These acids generally contain an average of about 18, or about 30, carbon atoms. Trimer acids are prepared by trimerizing one or more of the fatty acids described above. In one embodiment, tricarboxylic acid or its derivative is the reaction product of one or more unsaturated carboxylic acids, such as, an unsaturated fatty acid or alkenyl succinic anhydride and an alpha, beta unsaturated carboxylic reagent. Unsaturated carboxylic reagents include unsaturated carboxylic acids per se and functional derivatives thereof, such as anhydrides, esters, amides, imides, salts, acyl halides, and nitriles. The unsaturated carboxylic reagent includes mono-, di-, tri- or tetracarboxylic reagents. Specific examples of useful mono-basic unsaturated carboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, 2-phenylpropenoic acid, etc. Exemplary polybasic acids include maleic acid, maleic anhydride, fumaric acid, mesaconic acid, itaconic acid and citraconic acid. Generally, the unsaturated carboxylic reagent is maleic anhydride, acid ester or less, for example, those containing less than eight carbon atoms. In one embodiment, unsaturated dicarboxylic acid generally contains an average of about 12 to about 40, or about 18 to about 30 carbon atoms. Examples of such tricarboxylic acids include Empol® 1040, commercially available from Emery Industries, Hystrene® 5460 commercially available from Humko Chemical, and Unidyme® 60 commercially available from Union Camp Corporation.
[0117] [0117] In another embodiment, the corrosion inhibitor of the present invention comprises hydrocarbyl substituted carboxylic acid. Hydrocarbyl substituted carboxylic acids are prepared by reacting one or more olefins or polyalkenes with one or more of the unsaturated carboxylic reagents described above. The hydrocarbyl group generally contains about 30 to about 100 carbon atoms. In one embodiment, the hydrocarbyl group contains about 8 to about 40, or about 10 to about 30, or about 12 to about 24 carbon atoms. In one embodiment, the hydrocarbyl group can be derived from an olefin. The olefins typically contain about 3 to about 40, or about 4 to about 24 carbon atoms. Such olefins are preferably alphaolefins (sometimes referred to as mono-1-olefins or terminal olefins) or isomerized alpha-olefins. Examples of alpha-olefins include 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene , 1-eicosene, 1-heneicosene, 1-docosene, 1-tetracosene, etc. commercially available alpha-olefin fractions that can be used include C15-18 alpha-olefins, C12-C16 alpha-olefins, C14-16 alpha-olefins, C14-18 alpha-olefins, C16-18 alpha-olefins, alpha-olefins C16-20, C18-24 alpha-olefins, C22-28 alpha-olefins, etc. Hydrocarbyl-substituted carboxylic acids are described in U.S. Patent Nos. 3,219,666 and 4,234,435, the descriptions of which are incorporated herein by reference.
[0118] [0118] In another embodiment, the corrosion inhibitor of the present invention can be prepared by reacting one or more of the polyalkenes described above with an excess of maleic anhydride to provide the substituted succinic acid in which the number of succinic groups for each equivalent weight of the substituent group, i.e., polyalkenyl group, is at least about 1.3, preferably at least about 1.4, or more preferably, at least about 1.5. The maximum number will generally not exceed about 4.5 or, preferably, about 3.5. A suitable range is about 1.4 to about 3.5, or about 1.5 to about 2.5 succinic groups by equivalent weight of substituent groups.
[0119] [0119] Carboxylic acids are known in the art and have been described in detail, for example, below: U.S. patent number 3,215,707 (Rense); U.S. patent number 3,219,666 (Norman et al); U.S. patent number 3,231,587 (Rense); U.S. patent number 3,912,764 (Palmer); U.S. patent number 4,110,349 (Cohen); and U.S. patent number 4,234,435 (Meinhardt et al); and U.K. 1,440,219. The descriptions of these patents are incorporated by reference in this document. These patents are incorporated into this document as a reference for the description of carboxylic acids and methods for producing them.
[0120] [0120] In another embodiment, the corrosion inhibitor comprises the reaction product carboxylic acids described above with amines to form acylated amines. The amines can be monoamines or polyamines. Useful amines include those amines described in U.S. Patent No. 4,234,435 in Col. 21, line 4 Col. 27, line 50, these passages being incorporated by reference into this document. The amines can be any of the amines described above, preferably the amine is a polyamine, such as an alkylene polyamine or a condensed amine.
[0121] [0121] In one embodiment, carboxylic acid is present in situ as a by-product of the raw material used to produce a biologically derived oxygenated component or a by-product of extractors used to extract the biologically derived oxygenate from a fermentation broth.
[0122] [0122] In another embodiment, the polyamine is a grease diamine. Fatty diamines include mono- or dialkyl, symmetric or asymmetric ethylene diamines, propanodiamines (1,2, or 1,3), and polyamine analogs of the items mentioned above. Suitable commercial fatty polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S (N-soy-1,3-diaminopropane), Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O (N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available from AkzoNobel.
[0123] [0123] In another embodiment, the polyamines are polyoxyalkylene polyamines, for example, polyoxyalkylene diamines and polyoxyalkylene triamines. Preferred polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamines. Polyoxyalkylene polyamines are commercially available and can be obtained, for example, from Huntsman Corporation under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.". US 3,804,763 and 3,948,800 are expressly incorporated herein by reference for your description of such polyoxyalkylene polyamines and acylated products produced therefrom.
[0124] [0124] In another embodiment, polyamines are polyamines containing hydroxy. Polyamines containing monoamine hydroxy hydroxy analogs, particularly alkoxylated alkylenopolyamines, for example, N, N '- (dihydroxyethyl) ethylene diamines can also be used. Such polyamines can be produced by reacting the alkylene amines described above with one or more of the alkylene oxides described above. The similar alkylene oxide-alkanol amine reaction products can also be used, such as, the products produced by reacting the primary, secondary or tertiary alkanol amines described above with higher ethylene, propylene or epoxide in a molar ratio between 1 , 1 and 1,2. The reagent ratios and temperatures for carrying out such reactions are known to those skilled in the art. Specific examples of hydroxy-containing polyamines include N- (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, substituted mono (hydroxypropyl) -tetraethylene-pentamine, N - (3-hydroxybutyl) tetramethylenediamine, etc. The higher homologues obtained by condensing the polyamines illustrated above containing hydroxy through amino groups or through hydroxy groups are also useful. Condensation through amino groups results in a higher amine accompanied by the removal of ammonia, while condensation through hydroxy groups results in products containing ether bonds accompanied by the removal of water. Mixtures of two or more of any of the polyamines described above are also useful.
[0125] [0125] In another embodiment, the amine used in the preparation of the acylated amine corrosion inhibitor may be an alkylene polyamine. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, etc. Higher homologues and related heterocyclic amines, such as, piperazines and substituted N-amino alkyl-piperazines, are also included. Specific examples of such polyamines are ethylenediamine, triethylene tetramine, tris- (2-aminoethyl) amine, propylene diamine, trimethylenediamine, tripropylene tetramine, triethylene tetraamine, tetraethylenepentamine, hexaethyleneeptamine, pentaethyleneexamine, etc. The higher homologues obtained by condensing two or more of the alkyleneamines noted above are similarly useful as mixtures of two or more of the polyamines described above.
[0126] [0126] In one embodiment, the polyamine is an ethylene polyamine. Such polyamines are described in detail under the title Ethylene Amines in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Ethylene polyamines are often a complex mixture of polyalkylene polyamines that include cyclic condensation products.
[0127] [0127] Another useful polyamine is a condensation reaction between at least one hydroxy compound with at least one polyamine reagent that contains at least one primary or secondary amino group. The hydroxy compounds are preferably alcohols and polyhydric amines. In one embodiment, the hydroxy compounds are polyhydric amines. Polyhydric amines include any of the monoamines described above reacted with an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) which has two to about 20 carbon atoms, or two about four. Examples of polyhydric amines include diethanolamine, triethanolamine, tri- (hydroxypropyl) amine, tris- (hydroxymethyl) amino methane, 2-amino-2-methyl-1,3-propanediol, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine.
[0128] [0128] Polyamines that can react with alcohol or polyhydric amine to form condensation products or condensed amines are described above. The condensation reaction of the polyamine reagent with the hydroxy compound is conducted at an elevated temperature in the presence of an acid catalyst.
[0129] [0129] Amine condensates and methods for producing them are described in PCT publication WO86 / 05501 and U.S. patent number 5,230,714 (Steckel) which are incorporated by reference in their description for condensates and production methods.
[0130] [0130] The acylated amines and methods for preparing them are described in U.S. Patent Numbers 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; and 4,904,401. The descriptions of acylated nitrogen dispersants and other dispersants contained in these patents are incorporated by reference in this document.
[0131] [0131] In another embodiment, the corrosion inhibitor is a mixture comprising at least one dimer acid and at least one trimer acid.
[0132] [0132] In another embodiment, the corrosion inhibitor is a mixture comprising at least one dimer acid, at least one trimer acid and at least one alkyl dicarboxylic acid, preferably hexadecenyl succinic acid.
[0133] [0133] In another embodiment, the corrosion inhibitor is an amide formed by the reaction of unsaturated fatty acid and N-methyl glycine, such as, N-methyl-N- (1-oxo-9-octadecenyl) glycine.
[0134] [0134] In another embodiment, the corrosion inhibitor is the reaction product of linoleic acid or tall oil fatty acid with acrylic acid, such as, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6 -carboxy-4-hexyl-2-cyclohexene-1-octanoic.
[0135] [0135] In another embodiment, the corrosion inhibitor is a reaction product of unsaturated fatty acid and N- (2-hydroxyethyl) -1,2-diaminoethane, such as 1- (2-hydroxyethyl) -2- (8 -heptadecenyl) -2-imidazoline.
[0136] [0136] In a preferred embodiment, the corrosion inhibitor of the present invention comprises the reaction product of at least one dimer acid, at least one trimer acid, and at least one alkyl dicarboxylic acid, preferably hexadecenyl succinic acid, with a amine or diamine, preferably NH2 (CH2) n-NH-C8-10, where n is 1 to about 10. In a more preferred embodiment, the amine is N, N - dimethylcyclohexylamine.
[0137] [0137] In another embodiment, the corrosion inhibitor comprises, by weight, (a) about 35% to 70% of at least one alkenyl succinic mono- or di-acid in which the alkenyl group has 8 to 18 carbons; and (b) about 30% to 65% of an aliphatic or cycloaliphatic amine, diamine or polyamine containing 2 to 12 carbon atoms.
[0138] [0138] In another embodiment, the corrosion inhibitor comprises a composition having by weight (a) about 75% to 95% of at least one polymerized unsaturated aliphatic monocarboxylic acid, said unsaturated acid having 16 to 18 carbons per molecule , and (b) about 5% to 25% of at least one monoalkenyl succinic acid in which the alkenyl group has 8 to 18 carbons.
[0139] [0139] In another embodiment, the corrosion inhibitor comprises dodecenyl succinic acid (DDSA).
[0140] [0140] In yet another embodiment, the corrosion inhibitors of the present invention comprise at least one of the commercially available products listed in Tables 1 and 2. In Table 1, PTBE refers to pounds per thousand barrels of the denatured ethanol corrosion inhibitor. "PTB" in this document means "pounds per thousand barrels", a common term of the technique in the fuel additive industry. PTB is approximately equivalent to about 4 ppm. In yet another embodiment, the minimum amount or concentration of corrosion inhibitor or mixtures thereof is about 3 PTB and in another the amount is about 3 PTB to about 50 PTB, more preferably, an amount equal to or less than 30 ptb in finished oxygenated gasoline.
[0141] [0141] The current invention is intended to provide good protection against corrosion (ie NACE B + rating or better) after heat aging for at least 14 days, preferably for at least 30 days and, most preferably, for at least least 12 weeks.
[0142] [0142] The current invention is also intended to provide an oxygenated gasoline composition comprising at least two corrosion inhibitors, wherein the concentration of the total corrosion inhibitor is about 1 to about 50 ptb, or about 2 to about 50 ptb, or about 3.00 ptb to about 50 ptb and the composition has an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 1.00 to about of 3.00. In some embodiments, at least two corrosion inhibitors have an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 0.1 to about 2, or about 0.1 to about 1.
[0143] [0143] The current invention is also intended to provide an oxygenated gasoline composition comprising at least three corrosion inhibitors, wherein the concentration of the total corrosion inhibitor is about 1 to about 50 ptb, or about 2 to about 50 ptb, or about 3.00 ptb to about 50 ptb and the composition has an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 1.00 to about of 3.00. In some embodiments, at least three corrosion inhibitors have an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 0.1 to about 2, or about 0.1 to about 1.
[0144] [0144] The current invention is also intended to provide an oxygenated gasoline composition comprising at least four corrosion inhibitors, wherein the concentration of the total corrosion inhibitor is about 1 to about 50 ptb, or about 2 to about 50 ptb, or about 3.00 ptb to about 50 ptb and the composition has an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 1.00 to about of 3.00. In some embodiments, at least four corrosion inhibitors have an acid / amine equivalence ratio that ranges from about 0.1 to about 3, or about 0.1 to about 2, or about 0.1 to about 1.
[0145] [0145] In some embodiments, the invention provides an oxygenated gasoline composition comprising one or more corrosion inhibitors, wherein the concentration of the corrosion inhibitor is from about 0.5 ptb to about 7 ptb, about 0, 5 ptb to about 6 ptb, or about 0.5 ptb to about 5 ptb and where one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1:10 to about 1: 0 .
[0146] [0146] In some embodiments, the invention provides an oxygenated gasoline composition comprising about 1 to about 30% in v / v of a biologically derived alcohol renewable one or more corrosion inhibitors so that an anticorrosive and substantially renewable composition be formed. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof. In some embodiments, the concentration of the corrosion inhibitor is from about 0.5 ptb to about 7 ptb, about 0.5 ptb to about 6 ptb, or about 0.5 ptb to about 5 ptb. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1:10 to about 1: 0. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 0.1 to about 3.
[0147] [0147] In some embodiments of the invention, corrosion inhibitors have an acid: amine equivalence ratio of about 1:12 to about 1: 0, about 1:11 to about 1: 0, about 1 : 10 to about 1: 0, or about 1: 9 to about 1: 0. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 9. In other embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 0. In other embodiments, corrosion inhibitors have an acid: amine equivalence ratio of at least about 1:12, at least about 1:11, at least about 1:10, at least about 1: 9, at least about 1: 8, at least about 1: 7, at least about 1: 6, at least about 1: 5, at least about 1: 4, at least about 1: 3, at least about 1: 2, at least about 1: 1, or about 1: 0 (i.e., undetectable amine).
[0148] [0148] In some embodiments of the invention, one or more corrosion inhibitors have an amine nitrogen content of less than about 500 ppm, less than about 100 ppm, less than about 90 ppm, less than 80 ppm, less than about 70 ppm, less than about 60 ppm, or less than about 50 ppm. In some embodiments, one or more corrosion inhibitors have no detectable amines.
[0149] [0149] In some embodiments of the invention, one or more corrosion inhibitors comprise from about 1 to about 15% w / w, about 3 to about 13% w / w, about 5 to about 10% w / w, or about 6 to about 9% w / w of an alkyl or alkenyl carboxylic acid.
[0150] [0150] In some embodiments, one or more corrosion inhibitors comprising an alkyl or alkenyl carboxylic acid additionally comprise at least 50% w / w, at least 60% w / w, at least 70% w / w, at least 80 % w / w, at least 90% w / w, or about 50 to about 100% w / w, about 60 to 100% w / w, or about 70 to 100% w / w of at least one the mine.
[0151] [0151] BioTEC® 9881 (listed as Tec 9881 in Table 1) is an example of a commercially available corrosion inhibitor according to the invention, which is believed to contain about 60 to about 100% w / w alkyl amine , and about 5 to about 10% w / w of a long chain carboxylic acid.
[0152] [0152] In some embodiments of the invention, the concentration of one or more corrosion inhibitors in the oxygenated gasoline composition is about 0.5 ptb to about 7 ptb, about 0.5 ptb to about 6 ptb, about from 0.5 ptb to about 5 ptb, about 1 ptb to about 4 ptb, about 1 ptb to about 3 ptb, about 1 ptb to about 2 ptb, about 1.2 ptb, about 1, 4 ptb, about 1.6 ptb, or about 1.8 ptb.
[0153] [0153] In some embodiments of the invention, the concentration of one or more corrosion inhibitors in the oxygenated gasoline composition is from about 0.5 ptb to about 7 ptb, about 0.5 ptb to about 6 ptb, about from 0.5 ptb to about 5 ptb, about 3 ptb to about 5 ptb, about 3 ptb to about 4 ptb, about 3 ptb, about 4 ptb, or about 5 ptb.
[0154] [0154] The corrosion inhibitors of the present invention are useful with stocks of oxygenated gasoline mixtures that can be produced from a single component, such as the product from a refinery alkylation unit or other refinery streams. However, gasoline mixing stocks are most commonly mixed using more than one component. Gasoline blend stocks are mixed to meet the desired physical and performance characteristics and to meet regulatory requirements and can involve some components, for example, three or four, or can involve many components, for example, twelve or more.
[0155] [0155] Gasolines and gasoline blending stocks can optionally include other chemicals or additives. For example, additives or other chemicals can be added to adjust the properties of gasoline to meet regulatory requirements, add or increase desirable properties, reduce unwanted harmful effects, adjust performance characteristics or otherwise modify the characteristics of gasoline. Examples of such chemicals or additives include detergents, deposit control additives, antioxidants, stability optimizers, demulsifiers, corrosion inhibitors, metal deactivators, and others. More than one additive or chemical can be used.
[0156] [0156] Useful additives and chemicals are described in Colucci et al., U.S. patent number 5,782,937, which is incorporated by reference in this document. Such additives and chemicals are also described in Wolf, US patent number 6,083,228, and Ishida et al., US patent number 5,755,833, Schwahn US patent number 7,601,185, Wolf, WO 2010/091069, all of which are incorporated into reference title in this document. Gasolines and gasoline mixture stocks can also contain solvents or carrier solutions that are often used to release additives in a fuel. Examples of such solvents or carrier solutions include, but are not limited to, mineral oil, alcohols, carboxylic acids, synthetic oils, and numerous others that are known in the art.
[0157] [0157] In another embodiment, the corrosion inhibitors of the present invention can be formulated as part of a deposit control additive (DCA) package. Such a DCA may include the reaction products of certain aldehydes or ketones with the following conventional unmodified nitrogen-containing detergent additives described in US patent number 6,652,667: aliphatic hydrocarbyl substituted amines, hydrocarbyl substituted, substituted succiniminated poly (oxyalkylene) amines with hydrocarbyl, Mannich reaction products, polyalkylphenoxyaminoalkanes, nitro and aromatic polyalkylphenoxyalkan amino esters, carburetor / injector detergent additives that have a molecular weight in the range of 100 to 600 and that have a non-polar portion and polar portion containing nitrogen , or mixtures of these.
[0158] [0158] Amines substituted with aliphatic hydrocarbyl that can be used as reagents in the manufacture of deposit control additives are typically amines substituted with straight or branched chain hydrocarbyl that have at least one basic nitrogen atom and in which the hydrocarbyl group has an average numerical molecular weight of about 400 to 3,000. Preferred aliphatic hydrocarbyl-substituted amines include polyisobutenyl and polyisobutyl monoamines and polyamines. Such aliphatic hydrocarbyl amines can be prepared by conventional procedures known in the art. Suitable preparations are described in detail in U.S. patent numbers 3,438,757; 3,565,804; 3,574,576; 3,848,056; 3,960,515; 4,832,702; and 6,203,584, descriptions of these are incorporated by reference in this document.
[0159] [0159] Another class of reagents in the manufacture of DCA consists of hydrocarbyl-substituted poly (oxyalkylene) amines, also referred to as polyether amines. Hydrocarbyl-substituted poly (oxyalkylene) amines include poly (oxyalkylene) monoamines and hydrocarbyl polyamines where the hydrocarbyl group contains from 1 to about 30 carbon atoms, the number of oxyalkylene units will vary from about 5 to 100, and the amine moiety is derived from ammonia, a primary alkyl monoamine or secondary dialkyl monoamine, or a polyamine that has an amino terminal nitrogen atom. Preferably, the oxyalkylene portion will be oxypropylene or oxybutylene or a mixture thereof. Such hydrocarbyl-substituted poly (oxyalkylene) amines are described, for example, in U.S. Patent Numbers 6,217,624 and 5,112,364, the descriptions of which are incorporated herein by reference.
[0160] [0160] A preferred type of poly (oxyalkylene) monoamine substituted with hydrocarbyl is an alkyl phenyl poly (oxyalkylene) monoamine in which the poly (oxyalkylene) moiety contains oxypropylene units or oxybutylene units or mixtures of oxypropylene and oxybutylene units. Preferably, the alkyl group in the alkylphenyl moiety is a straight or branched chain alkyl of 1 to 24 carbon atoms. An especially preferred alkylphenyl moiety is tetrapropenylphenyl, that is, where the alkyl group is a branched chain alkyl group of 12 carbon atoms derived from propylene tetramer.
[0161] [0161] An additional type of hydrocarbyl-substituted poly (oxyalkylene) amine for use as reagents in the manufacture of the deposit control additives of the present invention consists of hydrocarbyl-substituted poly (oxyalkylene) aminocarbamates described, for example, in US patent numbers 4,288,612; 4,236,020; 4,160,648; 4,191,537; 4,270,930; 4,233,168; 4,197,409; 4,243,798 and 4,881,945, their descriptions are incorporated by reference in this document. Such poly (oxyalkylene) aminocarbamates contain at least one basic nitrogen atom and have an average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, and more preferably, about 1,000 to 3,000. A preferred aminocarbamate is alkylphenyl poly (oxybutylene) aminocarbamate in which the amine moiety is derived from ethylene diamine or diethylene triamine.
[0162] [0162] An additional class of reagents in the manufacture of the deposit control additives of the present invention consists of hydrocarbyl substituted succinimides. Typical hydrocarbyl-substituted succinimides include polyalkyl and polyalkenyl succinimides, wherein the polyalkyl or polyalkenyl group has an average molecular weight of about 500 to 5,000, and preferably about 700 to 3,000. Hydrocarbyl-substituted succinimides are typically prepared by reacting a hydrocarbyl-substituted succinic anhydride with an amine or polyamine that has at least one reactive hydrogen attached to an amine nitrogen atom. Preferred hydrocarbyl-substituted succinimides include polyisobutenyl and polyisobutanyl succinimides, and derivatives thereof. Hydrocarbyl-substituted succinimides are described, for example, in U.S. patent numbers 5,393,309; 5,588,973; 5,620,486; 5,916,825; 5,954,843; 5,993,497; and 6,114,542, and British patent number 1,486,144, the descriptions of which are incorporated herein by reference.
[0163] [0163] Yet another class of reagents in the manufacture of the deposit control additives of the present invention consists of Mannich reaction products that are typically obtained from Mannich condensation of a hydroxy-aromatic compound substituted with high molecular weight alkyl, an amine containing at least one reactive hydrogen, and an aldehyde. The hydroxy-aromatic compounds substituted with high molecular weight alkyl are preferably polyalkylphenols, such as polypropylphenol and polybutylphenol, especially polyisobutylphenol, in which the polyalkyl group has an average molecular weight of about 600 to 3,000. The amine reagent is typically a polyamine, such as alkylene polyamines, especially ethylene or polyethylene polyamines, for example, ethylene diamine, diethylene triamine, triethylene tetramine, and the like. The aldehyde reagent is usually an aliphatic aldehyde, such as, formaldehyde, paraformaldehyde, formalin, and acetaldehyde. A preferred Mannich reaction product is obtained by condensing a polyisobutylphenol with formaldehyde and diethylene triamine, where the polyisobutyl group has an average molecular weight of about 1,000. Mannich reaction products are described, for example, in U.S. Patent Nos. 4,231,759 and 5,697,988, descriptions of which are incorporated herein by reference.
[0164] [0164] Other reagents in the manufacture of the deposit control additives of the present invention are polyalkylphenoxyaminoalkanes, nitro and amino aromatic esters of polyalkylphenoxyalkanes, and mixtures of nitro and aromatic amino esters of polyalkylphenoxyalkanes and poly (oxyalkylene) amines substituted with hydrocarbons. Such mixtures are described in detail in U.S. Patent No. 5,749,929, the description of which is incorporated herein by reference.
[0165] [0165] Preferably, the detergent or deposit control additive compositions used in conjunction with the corrosion inhibitors of the present invention are the imine or tertiary amine products of the reaction between the reagents mentioned above and the aldehydes or ketones selected from below (less than 100) carbon number. Each of the unmodified deposit control additives described above contains a primary and / or secondary amine functionality, whose functionality can be modified by reacting with low carbon aldehydes or ketones that have the formulas: R16CHO, R16 CH2 CHO, R17 (C = O) R18 and R17 CH2 (C = O) R18, where R16, R17, and R18 can be the same or different and are each independently of a straight or branched chain hydrocarbyl or aryl group containing from 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Typically, a solvent, such as, isobutanol is employed in the reaction.
[0166] [0166] In a more preferred embodiment, the deposit control additive works synergistically with the corrosion inhibitors of the present invention to enhance corrosion protection and storage stability. Treatment rates for DCAs are preferably 27 to 45 ptb for one times the Lowest Additive Concentration. Two to four times this amount can be used up to a maximum preferred treatment rate of about 100 ptb.
[0167] [0167] In one aspect of the invention, corrosion protection and storage stability of the oxygenated gasoline composition is maintained for at least 2 weeks, preferably for 12 weeks, more preferably, for 120 days.
[0168] [0168] Other conventional components and assistants that can be used are antioxidants, such as, butylated hydroxytoluene, 2,4-Dimethyl-6-tert-butylphenol, 2,6-Di-tert-butylphenol (2,6-DTBP), pphenylenediamine, diaryl amines, bis (octylphenyl) amine, N, N'-di-sec-butyl-pphenylenediamine, ethylene diamine; or stabilizers, for example, based on amines, such as, p-phenylenediamine, N, N-dimethylcyclohexylamine, dicyclohexylamine or derivatives thereof, and phenols such as 2,4-di-tert-butylphenol or 3,5-di-tertic acid -butyl-4-hydroxyphenylpropionic; turbidity-reducing additives (dehazers), demulsifiers, antistatic agents, metallocenes, such as, ferrocene or methylcyclopentadienyl manganese tricarbonyl, lubricity additives, such as, certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines and hydroxyacetamines and hydroxyacetamines ; anti-knock additives, such as, tetraethyl lead, methylcyclopentadienyl manganese tricarbonyl (MMT), ferrocene, pentacarbonyl iron, toluene, isooctane, triptan, antifreeze additives, ethers, such as methyl tert-butyl ether, tertiary methyl ether , tertiary butyl ethyl ether, tertiary amyl ethyl ether, diisopropyl ether, octane requirement additives, lead scavengers (for leaded gasoline) including tricresyl phosphate (TCP), 1,2-Dibromoethane, 1,2-Dichloroethane; and also colorants that include Solvent Red 24, Solvent Red 26, Solvent Yellow 124, Solvent Blue 35.
[0169] [0169] Gasoline blending stocks suitable for use in the method of this invention are typically blending stocks useful for producing gasolines for consumption in spark ignition engines or other engines that burn gasoline. Suitable gasoline blending stocks include gasoline blending stocks that meet ASTM D4814 and reformed gasoline blending stocks. Suitable gasoline blending stocks also include blending stocks that have a low sulfur content, which may be desired to meet regional requirements that have, for example, less than about 150, preferably less than about 100 and, more preferably, less than about 80, or less than about 30, or less than about 10 parts per million parts per volume of sulfur. Such suitable gasoline blending stocks also include blending stocks that are low in aromatics, which may be desirable to meet regulatory requirements, for example, which are less than about 8000 and, preferably, less than about 7000, or less than about 6,200, or less than about 4,000 parts per million parts per volume of benzene.
[0170] [0170] An oxygenate, such as methanol, ethanol, butanol, or mixtures of these, is mixed with the gasoline mixture stock. In that case, the resulting gasoline mixture includes a mixture of one or more gasoline mixture stocks and one or more suitable oxygenates. In another embodiment, one or more isomers of butanol can be mixed with one or more gasoline mixture stocks and, optionally, with one or more suitable oxygenates, such as ethanol. In such an embodiment, one or more gasoline mixture stocks, one or more isomers of butanol and, optionally one or more suitable oxygenates can be mixed in any order. For example, a butanol can be added to a mixture, which includes a mixture of suitable gasoline and oxygenated mixtures. As another example, one or more suitable oxygenates and a butanol can be added in several different locations or in multiple stages. For further examples, a butanol, more preferably, isobutanol, can be added to the appropriate oxygenates, added before the appropriate oxygenates or mixed with the appropriate oxygenates before being added to a gasoline mixture stock. In a preferred embodiment, a butanol, more preferably, isobutanol, is added to the oxygenated gasoline. In another preferred embodiment, one or more suitable oxygenates and a butanol can be mixed in a gasoline mixing stock simultaneously.
[0171] [0171] In any such embodiment one or more butanols and, optionally one or more suitable oxygenates can be added at any point along the distribution chain. For example, a gasoline mixture stock can be transported to a terminal and then a butanol and, optionally one or more suitable oxygenates can be mixed with the gasoline mixture stock, individually or in combination, at the terminal. As an additional example, one or more gasoline mixture stocks, one or more isomers of butanol and, optionally one or more suitable oxygenates can be combined in a refinery. Other components or additives can also be added at any point in the distribution chain. In addition, the method of the present invention can be practiced at a refinery, terminal, retail location, or any other suitable point in the distribution chain.
[0172] [0172] The oxygenates of the present invention can arise or be provided in many qualities or grades, such as commercial grade or fuel, as well as pure grade or reagent, and can be derived from any source, such as, but not limited to a, oil refinery chains, distillation cuts, and biologically derived biobutanol (for example, bioethanol, corn or other renewable crops or substrates).
[0173] [0173] In one embodiment, the oxygenates of the oxygenated gasoline composition of the present invention comprise at least 5% renewable component. In a preferred embodiment, said renewable component comprises biologically derived ethanol, biologically derived butanol or mixtures thereof.
[0174] [0174] In some embodiments, the oxygenate is inhibited against corrosion. The corrosion inhibited oxygenate can have about 90 to about 100% w / w of an alcohol and about 10 to 200 ptb of a corrosion inhibitor. In some embodiments, the corrosion inhibitor can be any of the corrosion inhibitors discussed in this document. In some embodiments of the invention, corrosion inhibitors have an acid: amine equivalence ratio of about 1:12 to about 1: 0, about 1:11 to about 1: 0, about 1:10 to about 1: 0, or about 1: 9 to about 1: 0. In some embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 9. In other embodiments, one or more corrosion inhibitors have an acid: amine equivalence ratio of about 1: 0. In other embodiments, corrosion inhibitors have an acid: amine equivalence ratio of at least about 1:12, at least about 1:11, at least about 1:10, at least about 1: 9, at least about 1: 8, at least about 1: 7, at least about 1: 6, at least about 1: 5, at least about 1: 4, at least about 1: 3, at least about 1: 2, at least about 1: 1, or about 1: 0 (i.e., undetectable amine). In some embodiments, alcohol is biologically derived. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof.
[0175] [0175] In some embodiments, such corrosion-inhibited oxygen is used in a method for producing oxygenated gasoline. In some embodiments, the method includes mixing the corrosion-inhibited oxygenate with the base gasoline stock to produce oxygenated gasoline. In some embodiments, the corrosion-inhibited oxygenate comprises an alcohol that is biologically derived. In some embodiments, alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and mixtures thereof.
[0176] [0176] Preferably, the oxygenated gasoline according to the invention can be manufactured from existing fuel mixtures. One of these mixtures could be an E85 fuel with a proportion of 70 to 85% by volume of ethanol and 15 to 30% by volume of base fuel. The other blend could comprise 30 to 60% by volume of base fuel and 40 to 70% by volume of at least one butanol isomer, preferably isobutanol. Both of these mixtures can be mixed together to produce oxygenated gasoline fuel which comprises about 15 to 70% by volume of base fuel, about 5 to 65% by volume of ethanol and about 5 to 50% of butanol, in particular isobutanol .
[0177] [0177] In one embodiment, oxygenated gasoline comprises an amount equal to or less than 5% in v / v of methanol.
[0178] [0178] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 10% in v / v of ethanol.
[0179] [0179] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 20% in v / v of ethanol.
[0180] [0180] In another embodiment, the oxygenate comprises an amount equal to or less than 30% in v / v of ethanol.
[0181] [0181] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 10% in v / v of butanol.
[0182] [0182] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 20% in v / v of butanol.
[0183] [0183] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 30% in v / v of butanol.
[0184] [0184] In another embodiment, oxygenated gasoline comprises an amount equal to or less than 40% in v / v of butanol.
[0185] [0185] In another embodiment, oxygenated gasoline comprises about 16% v / v of butanol.
[0186] [0186] In another embodiment, oxygenated gasoline comprises about 24% v / v of butanol.
[0187] [0187] In a preferred embodiment, the oxygenated gasoline mixture comprises at least about 10 percent by volume, more preferably at least about 16 percent by volume and most preferably at least about 24 percent by volume. at least one butanol isomer.
[0188] [0188] Although the corrosion inhibitors used in this document will, in general, be added to an oxygenated gasoline, they can also be formulated as a concentrate that uses at least one organic solvent. The corrosion-inhibiting composition of the present invention can be prepared in the form of a solvent solution in which the solvent comprises from about 15 to 65% by weight of the composition. Suitable solvents are usually liquid organic compounds that boil in the boiling range of hydrocarbon fuel, in particular hydrocarbons and alcohols and include hexane, cyclohexane, heptane, octane, isooctane, benzene, toluene, xylenes, methanol, ethanol, propanol, butanol, gasolines , jet fuels, kerosene and the like. Solvent mixtures can also be used. In some embodiments of the invention, a mixture of xylenes and ethyl benzenes is used with a corrosion inhibitor.
[0189] [0189] Preferably, an aromatic hydrocarbon solvent (such as toluene, xylenes or high-boiling aromatics or aromatic diluents and the like) is used. Aliphatic alcohols containing 3 to 8 carbon atoms (such as isopropanol, isobutylcarbinol, n-butanol and the like), alone or in combination with hydrocarbon solvents can also be used.
[0190] [0190] Alcohol solvents mono- or poly (oxyalkylene) alkoxy solvents for use in the formulation of corrosion inhibitors include, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, 1-methoxy-2-propanol , 1-ethoxy-2-propanol, 1-n-butoxy-2-propanol, diethylene glycol methyl ether, diethylene glycol butyl ether, propylene ethylene glycol methyl ether, propylene ethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether and the like that include mixtures thereof. A preferred mono- or poly (oxyalkylene) alkoxy alcohol is 2-n-butoxyethanol. A commercial 2-n-butoxyethanol or ethylene glycol mono-butyl ether is available as EB Butyl Cellusolve from Dow Chemical Company.
[0191] [0191] Suitable aliphatic solvents also include disarmated solvents such as Exxsol D40 and D60 available from ExxonMobil, other aliphatic solvents such as D15-20 Naphtha, D115-145 Naphtha and D31-35 Naphtha also available from ExxonMobil and non-aromatic mineral spirits and the like .
[0192] [0192] Excessive acid components such as acetic acid and sulfuric acid species are known to contribute to wear and deposit build-up in engines and / or valves or other engine parts. Dispersants can be used to help raise the pH of oxygenated gasoline slightly by buffering the acetic and / or sulfuric acid components that buffer the acetic and / or sulfuric acid components, thereby reducing or preventing the formation of reaction products that contribute to deposit. The dispersant, when used, will also be useful in buffering acid corrosion inhibitors.
[0193] [0193] It is preferred that the acid-to-amine equivalence ratio in the corrosion-inhibited oxygenated gasoline composition is in the range of about 1 to about 3, preferably about 1 to about 2, more preferably about 1. In other embodiments, the one or more corrosion inhibitors in the oxygenated gasoline composition have an acid to amine equivalence ratio in a range of about 0.1 to about 3, about 0.1 to about 2 or about 0.1 to about 1. Primary, secondary or tertiary aliphatic monoamines can be used to adjust the ratio of amine equivalence to carboxylic acid. Such primary amines include, but are not limited to, butyl amine, hexyl amine, octyl amine, ndodecyl amine, n-tetradecyl amine, n-hexadecylamine, lauryl amine, myristyl amine, palmitil amine, stearyl amine and oleyl amine, cetylamine, N- Tetradecylamine Cocoamine, Alkyl (unsaturated C16 and C18) amine, Alkyl (C14 to 18) amine, Alkyl (C16 to 22) amine, Alkyl (unsaturated C8 to 18 and C18) amine, Alkyl (C12 to 18) amine. Other primary commercially available amines include coconut oil amine, tallow amine, hydrogenated tallow amine and cottonseed oil amine.
[0194] [0194] Examples of secondary and tertiary amines that can be used include, but are not limited to, dibutylamine, Dicyclohexylamine, N, N-dimethylcyclohexylamine, Di (hydrogenated tallow) amine, Dicocoalkyl amine, Dialkyl (C14 to 18) amine, Dialquil ( C12 to 18) amine, Dialkyl (C16 to 22) amine, N-Tridecyltridecanamine, N-Methylstearylamine, Diestearyl amine, Dialkyl (C8 to 20) amine, N-Octadecylbenzylamine, NIsopropyloctadecylamine, N-Hexadecyloctecymethylamine, Dimantineamine, Dimantine Cocodimethylamine, Alkyl (C10 to 16) dimethyl amine, Alkyl (C14 to 18) dimethyl amine, Alkyl (unsaturated C16 to 18 and C18) dimethyl amine, Alkyl (C16 to 18) dimethyl amine, Alkyl (C12 to 18) dimethyl amine, Alkyl (C16 to 22) dimethyl amine, Oleyldimethylamine, N-Methyldidecylamine, N, N-Dioctylmethylamine, Dicocomethylamine, dihydrogenated sebomethyl amine, Trialquil (C6 to 12) amine, N, N-Dioctyl amyl, Trialquil (C8 to 10) amine, Cocopropylenediamine, Laurylpropylenediamine, N-Dodecylpropylenediamine, Lau rilamine dipropylenediamine, N- (Tallet alkyl) dipropylenetriamine, N- (Tallet alkyl) dipropylenetriamine, N-Stearoiltetraethylenetetramine, octyl dimethyl amine, octadecyl dimethyl amine, octadecyl methyl benzyl amine, hexylethyl amine, triethylethylamine, trichlorethylamine, trichlorethylamine can also be used.
[0195] [0195] The acid / amine equivalence ratio can be determined by any method known in the art. EXAMPLES
[0196] [0196] The present invention will be explained in more detail below by reference to the following examples. However, the invention should not be construed as being limited to them.
[0197] [0197] Not all commercial corrosion inhibitors provide corrosion protection for mixtures of alcohol with gasoline alcohol (such as isobutanol and methanol / cosolvent) after aging for significant periods of time (for example, 30 days to 12 weeks) at elevated temperature ( for example, 43.3 ºC (110 ºF). Aging at 43.3 ºC (110 ºF) is a test for performance during long-term ambient storage (for example, 1 year). It has been unexpectedly found that different alcohols respond differently to a corrosion inhibitor and that simply increasing amounts of corrosion inhibitor does not necessarily provide better protection against corrosion. It has also been found unexpectedly that certain corrosion inhibitors provide superior corrosion protection and can provide corrosion protection at low concentrations, which are more economical and preferred.
[0198] [0198] A test by the National Association of Corrosion Engineers (NACE) for corrosion inhibitors according to the invention is shown below.
[0199] [0199] NACE TM0172-2001 - Determination of Corrosive Properties of Loads in Oil Product Pipelines provides a uniform method of testing the corrosive properties of oil product pipeline loads and is used in this document to test corrosion properties of the oxygenated gasoline of the present invention. NACE TM0172-2001 is incorporated entirely into this document as a reference. In this test method, the surface of a cylindrical steel test specimen is prepared and then immersed in a mixture of the test fuel and distilled water. The mixture is stirred and maintained at a prescribed temperature. The test specimen is then classified by the proportion of the test surface that has been corroded. Experience has shown that if sufficient inhibitor is present to produce B + or better results as defined in this standard, general corrosion in flowing pipelines can be controlled. EXAMPLES 1 TO 20
[0200] [0200] The following examples use unleaded unleaded gasoline that meets the requirements of the ASTM D4814 Standard Specification for Automotive Spark Ignition Engine Fuel with the exception of displaying a “C” rating or worse by the NACE TM0172-2001 standard as the gasoline mixing component. Oxygenated fuel which represents the common production of a manufacturing plant process for blending with gasoline for use as automotive spark ignition engine fuel is used as the oxygenated fuel blending component. The desired gasoline / oxygenated fuel ratio with the candidate corrosion inhibitor using the recommended treatment value is mixed.
[0201] [0201] The corrosion classification with the NACE TM0172-2001 test method is determined. The mixture of fuel with candidate corrosion inhibitor that conforms to a NACE Standard Test classification of B + (less than 5% of surface rust) or better for the applied treatment value is considered acceptable. The treatment value used in this invention may vary from the recommended treatment value. Preferably, the total corrosion inhibitor concentration is about 8.55 to about 142.5 mg / l (about 3 to about 50 pounds per thousand barrels) of the oxygenated fuel mixture. More preferably, it is about 8.55 to about 57 mg / l (about 3 to about 20 pounds per thousand barrels) of the oxygenated fuel mixture and more preferably an amount of 42.75 mg / l or less (15 ptb).
[0202] [0202] The corrosion classification by the use of NACE TM0172-2001 of the same ratio of gasoline / oxygenated fuel mixture is determined after 14 days, 30 days or 12 weeks of storage at 43.3 ºC (110 ºF). The fuel mixture with candidate corrosion inhibitor again corresponds to the NACE Standard Test classification of B + (less than 5% surface rust) or better after at least 14 days of storage, preferably after 30 days and preferably after at least 12 weeks is considered acceptable. The samples are stored under laboratory conditions at 43.3 ºC (110 ºF) in a non-metallic container protected from UV light and that obeys all safety precautions.
[0203] [0203] Table 3 shows NACE test results for gasoline containing either a mixture of methanol or isobutanol co-solvent with common buffered corrosion inhibitors. Although DCI-11 and Nalco 5624A provide protection against corrosion by aging with 12-week heating for the methanol-cosolvent mixture, both fail to provide good protection for the isobutanol mixture. This is unexpected in that isobutanol should be more like conventional gasoline and common corrosion inhibitors should provide good protection.
[0204] [0204] Table 4 shows different heat aging behavior for similar mixtures by using corrosion inhibitor processing levels close to the recommended maximum. Unexpectedly, these higher processing levels do not provide protection for either the methanol-cosolvent mixture or the isobutanol mixture for 12 weeks.
[0205] [0205] Table 5 shows NACE test results after 14 day heat aging.
[0206] 1. Densidade de gasolina a 15,55 ºC (60 ºF) em relação à densidade da água a 15,55 ºC (60 ºF). 2. Destilação –Método ASTM D86 3. ml – mililitros evaporados [0206] Table 6 contains data on date composition in the base gasoline used in the examples.
[0207] [0207] Abstract: The corrosion performance of three commercial corrosion inhibiting additives in gasoline mixtures was evaluated by the Standard Test Method TM0172 of the National Association of Corrosion Engineers (NACE) - Determination of Corrosive Properties of Loads in Product Pipelines of Petroleum. Base gasoline and mixtures using two different oxygenated mixtures were tested. All mixtures offered acceptable performance both in fresh mixtures and in mixtures aged by heating for up to 12 weeks at 43.3 ºC (110 ºF), thus indicating satisfactory performance of the additives.
[0208] a. Afton BioTEC® 9880 b. Afton BioTEC® 9881 c. Lubrizol® 541
[0209] 1. Preparar quantidades suficientes de combustíveis de teste para testes NACE frescos e envelhecidos. 2. Realizar teste NACE em combustíveis frescos. 3. Envelhecer amostras de combustível de teste adicionais a 43,3 ºC (110 ºF) por 30 dias. 4. Realizar teste NACE em combustíveis envelhecidos por 30 dias. 5. Envelhecer amostras de combustível de teste adicionais a 43,3 ºC (110 ºF) por 12 semanas. 6. Realizar teste NACE em combustíveis envelhecidos por 12 semanas. [0209] The NACE Standard Test Method TM0172 - Determination of Corrosive Properties of Loads in Petroleum Product Pipelines (NACE test) was used to evaluate corrosion performance in all samples. The samples consisted of fresh preparations of the Gasoline / Alcohol fuel mixtures with additive, as well as identical preparations that were subsequently aged by heat before the NACE test. Heat-aged samples were aged in glass vials lined with plastic with Teflon linings on the plastic lids. The heat aging vials were submerged in the water of a controlled bath at 43.3 ºC (110 ºF). PROCEDURE 1. Prepare sufficient quantities of test fuels for fresh and aged NACE tests. 2. Perform NACE test on fresh fuels. 3. Aging additional test fuel samples at 43.3 ºC (110 ºF) for 30 days. 4. Perform NACE test on fuels aged for 30 days. 5. Aging additional test fuel samples at 43.3 ºC (110 ºF) for 12 weeks. 6. Perform NACE test on fuels aged for 12 weeks.
[0210] [0210] Results: Three commercially available corrosion inhibitors registered with the EPA were tested in specific concentrations: Afton BioTEC® 9880 at 4.56 mg / l, Afton BioTEC® 9881 at 11.4 mg / l and Lubrizol® 541 at 11.4 mg / l. All fresh fuel mixtures provided NACE ratings of A (without rust). After heat aging for 30 days and 12 weeks, all mixtures provided acceptable NACE ratings of B + or better, in the range of B + (2% rust) to A (no rust). A NACE rating of B + in a fresh mix is generally required by the common transport pipeline fuel specifications. The non-additive base fuel provided a NACE rating of C (30% rust) for both fresh and heat-aged samples. The results are summarized in Table 9.
[0211] [0211] Afton BioTEC® 9880, Afton BioTEC® 9881 and Lubrizol® 541 all provided superior corrosion protection performance, resulting in fuel mixtures that provided acceptable NACE ratings of B + or better after heat aging for 30 days and 12 weeks, which indicates that these corrosion inhibitors will provide corrosion protection for long term ambient storage of fuel mixtures. In addition, these inhibitors provide sufficient protection against corrosion at low treatment values below 14.25 mg / l (5 ptb), which makes them more economical. Effective corrosion inhibitors comprise alkenyl succinic acid where alkenyl groups are tetrapropenyl isomers without amine neutralization (Afton BioTEC® 9880) or with about 9 equivalents of amine neutralization such as N, N-dimethyl cyclohexyl amine (Afton BioTEC® 9881) or an amine-neutralizing bis ester where the ester bond is a glycol as described in Patent no. US 3,177,091 (Lubrizol® 541). EXAMPLES 28 TO 33
[0212] [0212] Lubrizol® 541 in combination with BioTEC® 9880 and a high dose (42.75 mg / l (15 ptb)) of BioTEC® 9881 were also tested according to the procedure described above for Examples 21 to 27. The data for these additional tests are summarized in Table 10.
[0213] [0213] Table 10 also shows that Afton BioTEC® 9880, Afton BioTEC® 9881 and Lubrizol® 541 provided protection against corrosion, resulting in fuel mixtures that provide acceptable NACE ratings of B + or better after heat aging for 30 days and 12 weeks. Although the highest treatment value of 42.75 mg / l (15 ptb) of BioTEC® 9881 resulted in fuel mixtures that have acceptable NACE ratings, the lowest treatment values of 11.40 mg / l (4 ptb) of Lubrizol® 541 and 4.56 mg / l (1.6 ptb) of BioTEC® 9880 added or individually or in combination also obtained acceptable NACE ratings. A high treatment value of BioTEC® 9881 did not impair performance (compare tests 32 and 33 with 9, 10, 11, 12) as observed for other additives. The combinations of Lubrizol 541 with BioTEC® 9880 did not exhibit antagonism that would impair performance (compare 30 and 31 with 22, 23, 28 and 29). EXAMPLES 34 TO 48
[0214] [0214] Additional tests were performed using Lubrizol® 541, BioTEC® 9880 and BioTEC® 9881 according to the procedure described above for Examples 21 to 27. The data for these additional tests are summarized in Tables 11 and 12.
[0215] [0215] Table 11 shows Lubrizol 541, BioTEC 9880 and BioTEC 9881 which provide protection against corrosion after 30 days of heat aging in a strong base gasoline (gasoline 3) for both methanol / co-solvent and iso- butanol, while Table 12 shows BioTEC 9880 and BioTEC 9881 which provide protection against corrosion after 12 weeks of heat aging in a less strong base gasoline (gasoline 4).
[0216] [0216] Fuel additive chemicals are known to be insoluble in high concentrations of oxygenates such as polyisobutylene amine (PIBA) in high concentrations of ethanol. It is desired that the combination of corrosion inhibitors of the present invention at the desired treatment values are completely soluble. The Modified MOBIL Filterability test or an equivalent test that correlates to real-world data can be used to test for solubility.
[0217] [0217] From the above description, it is apparent that the objectives of the present invention have been achieved. Although only certain realizations have been described, realizations and various modifications will be apparent from the description above for those skilled in the art and are within the spirit and scope of the present invention.
[0218] [0218] All publications, patents and patent applications mentioned in that specification are indicative of the level of technique of those versed in the technique to which this invention belongs and are incorporated into this document for reference to the extent that each publication, patent or individual patent application was specifically and individually indicated to be incorporated by reference for all purposes.

权利要求:
Claims (7)
[0001]
COMPOSITION OF OXYGENED GASOLINE having improved corrosion properties, characterized by comprising: a gasoline mixing component, 2 to 30% v / v isobutanol, and an amount of one or more corrosion inhibitors, wherein said amount is 2.85 mg / l (1 ptb) to 11.41 mg / l (4 ptb) a) wherein said one or more corrosion inhibitors comprise hydrogenated tallow alkylamine, N, N-dimethylcyclohexylamine, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-4-hexyl- 2- cyclohexene-1-octanoic, DCI-6A, Tolad 249 or dodecenyl succinic acid and in which said one or more corrosion inhibitors have an acid / amine equivalence ratio of 0.1 to 3, or b) in which said one or more corrosion inhibitors are BioTEC 9880, BioTEC 9981 or Lubrizol 541.
[0002]
COMPOSITION according to claim 1, characterized in that it comprises 16% v / v isobutanol or 24% v / v isobutanol.
[0003]
COMPOSITION according to any one of claims 1 to 2, characterized in that isobutanol is biologically derived isobutanol.
[0004]
COMPOSITION according to any one of claims 1 to 3, characterized in that it further comprises ethanol.
[0005]
COMPOSITION according to any one of claims 1 to 4, characterized in that it additionally comprises one or more deposit control additives.
[0006]
COMPOSITION according to any one of claims 1 to 5, characterized in that it additionally comprises one or more antioxidants, detergents, stability optimizers, demulsifiers or metal deactivators.
[0007]
CORROSION REDUCTION METHOD IN AN INTERNAL COMBUSTION ENGINE and in fuel infrastructure systems, characterized by comprising operating the internal combustion engine or the fuel infrastructure system with the oxygenated gasoline composition as defined in any one of claims 1 to 6.

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-04| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-12-24| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-10-19| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

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2022-02-08| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2650 DE 19-10-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161581902P| true| 2011-12-30|2011-12-30|

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US61/581,902|2011-12-30|

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PCT/US2012/000591|WO2013101256A2|2011-12-30|2012-12-28|Corrosion inhibitor compositions for oxygenated gasolines|

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