Classifications

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  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/12—Inorganic compounds
  • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
  • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/12—Inorganic compounds
  • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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  • C10L1/1857—Aldehydes; Ketones
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
  • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
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  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
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  • C10L1/224—Amides; Imides carboxylic acid amides, imides
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring

Definitions

• the present invention relates to novel compositions of ingredients that are used as additives for liquid fuels 1 , to produce clear and stable solutions with the fuels that meet or exceed the specifications of the fuels and that substantially improve the combustion of the fuels, reducing consumption of the fuel and emissions of carbon monoxide (CO) and unburned hydrocarbons (HC), formation of fumes, particles and carbonaceous deposits.
• the composition of the additives includes an aqueous solution of one or more amino-acids and alcohols having 1 to 5 carbon atoms, and optionally reaction products of acids and basic nitrogenated products, methyl esters of fatty acids and/or solvents. These compositions can also include additives for improving the octane and cetane numbers.
• Patent US 4,045,188 recommends as a stabiliser an additive for hydrocarbon motor fuels for internal combustion engines which consists of mixtures of ditertiarybutyl peroxide and tertiarybutyl alcohol. Certain fuel economy improvements were found at the recommended treatment levels.
• Patent US 4,298,351 recommends using a composition consisting of methanol and 7-25% of a tertiary alkyl peroxide. This composition can be used as a gasoline substitute as well as in mixture with conventional gasolines.
• the self-ignition problems in conventional gasoline engines were solved by incorporating water and isopropanol.
• the use of alcohol in these formulations can produce undesired effects such as promoting corrosion, water absorption, etc.
• Patent EP 0255115 recommends the use of a gasoline additive composition consisting of an organic peroxide such as di-tertiary butyl peroxide, a detergent selected from among amines, diamines, polymeric amines with carboxylic acids and a suitable hydrocarbonated solvent.
• an organic peroxide such as di-tertiary butyl peroxide
• a detergent selected from among amines, diamines, polymeric amines with carboxylic acids and a suitable hydrocarbonated solvent.
• water is introduced in the combustion chamber as steam and not dispersed in the fuel. This requires using a special device attached to the engine.
• Patent US 5,156,114 claims the use of liquid fuels containing about 20 to about 80% water in internal combustion engines. This solution also requires modifying the engine, installing a catalyst in the combustion chamber to produce hydrogen from at least one part of water introduced together with the organic fuel. The hydrogen formed is burned with the organic fuel. The resulting excess power, together with the excess power resulting from the expansion of the vapour, fully compensates the loss of power due to the lower amount of organic fuel.
• This patent mainly addresses the use of aqueous methanol or ethanol as fuels, presenting no homogeneity problems as both of these organic compounds are completely miscible with water.
• the author also refers to the use of aqueous liquid hydrocarbonated fuels, and emphasises that the fuel must be an emulsion and that two pipes must be fitted in the engine to prevent undesirable water condensation. It describes in a general manner the type of commercially available surfactants that would be necessary to help dispersion of water in the liquid fuel, in the scope of the invention.
• One of the disadvantages of this solution is that the engine must be altered.
• Another more serious disadvantage is that when the engine is operated using a fuel that is fully miscible with water (that is, alcohol or aqueous alcohol) or with a fuel that is not miscible with water (such as a hydrocarbon or an emulsion of water in the hydrocarbon) the resulting mixture of the two types of fuel immediately causes stability problems and operational problems.
• a fuel that is fully miscible with water that is, alcohol or aqueous alcohol
• a fuel that is not miscible with water such as a hydrocarbon or an emulsion of water in the hydrocarbon
• Patent WO 0069999 describes an additive for stabilizing water-containing fuels, consisting of an alcohol with 5 to 10 carbon atoms, 0.5 to 3 parts by weight for each part of said alcohol, an carboxylic amide with 5 to 10 carbon atoms and 3 to 10 parts by weight for each part of said alcohol of a carboxylic acid with 5 to 10 carbon atoms.
• the additive represents between 5-15% by weight of the liquid fuel.
• additives for fuels of internal combustion engines and boilers that include water, capable of improving combustion, reducing the formation of fumes, particles and carbonaceous residues and reducing the consumption of the fuel, can be obtained by a simple mixture of: a) an aqueous solution of one or more aminoacids; and b) one or more alcohols containing between 1 and 5 carbon atoms; and optionally c) reaction products of acids and basic nitrogenated compounds; and/or d) methyl esters of fatty acids; and/or e) solvents compatible with the fuel.
• the formulation of the additives it is possible to include compounds for improving the octane and cetane numbers.
• the additives object of the invention are miscible with fossil fuels of petroleum origin and with bio-diesel oils (methyl or ethyl esters of fatty acids), and show no problems of instability or separation of the phases.
• the concentration of aminoacids in the solution a) can vary greatly, generally between 1.10 -4 molar and 1.10 -1 molar, preferably between 1.10 -4 and 1.10 -2 molar.
• the solution can be prepared using drinking water, but it is preferable to use demineralised or distilled water.
• the aminoacids can be used the aminoacids or mixtures thereof described for example in the Encyclopaedia of Chemical Processing and Design, vol. 3, p. 197-256, John J. McKetta Eds., 1977. Particularly advantageous in the scope of the present invention are histidine, phenylalanine, tryptophan and tyrosine.
• alcohols b) can be used alcohols with 1 to 5 carbon atoms or their mixtures; specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propane, 1,1-dimethylethanol, 1-pentanol, etc.
• the ration by weight of the solution a) and the alcohols b) can vary greatly, and mainly depends on the nature of the alcohols or mixtures thereof. It is mainly chosen in order to obtain a good miscibility of the additive in the hydrocarbonated fuel employed, although these alcohols obviously improve combustion per se because of the oxygen they supply.
• weight ratios a)/b) can be used of between 0.5/99.5 and 50/50, and more preferably between 2/98 and 25/75.
• the additives object of this invention can optionally include a third component c) consisting of the reaction products of acids and basic nitrogenated products.
• acids can be used acids with the general formula R-COOH, where R is an alkyl or alkenyl group with 10-36 carbon atoms, particularly fatty acids or dimers of fatty acids.
• basic nitrogenated compounds can be used ammonia, hydrazines, urea, ethanolamine, diethanolamine, triethanolamine, primary amines such as butylamine, cyclohexylamine, hexadecylamine aniline, etc., secondary amines such as di-n-butylamine, di-n-hexylamine, etc., tertiary amines such as tri-n-butylamine, and polyamines such as diethylentriamine, triethylentriamine, tetraethylenpentamine, etc.
• the reaction of the acid and the amine can take place according to known methods, such as by heating the mixture of acids and amines to temperatures of 100-250°C in the presence or absence of inert solvents.
• the amount of component c) used is not critical and it is chosen to improve the compatibility of the components a) and b) with the fuel and to give it anticorrosive properties. Generally sufficient are amounts that, considering the amount of additive in the fuel, provide concentrations of said component c) in the fuel of between 100 and 10,000 ppm.
• the additives object of the invention can contain a fourth component d) consisting of methyl esters of fatty acids, which enhance lubricity and provide oxygen to improve combustion.
• the amount of component d) is not critical.
• the additives object of the invention can contain a fifth component e), a solvent compatible with the fuel, which is used to improve the compatibility of the other components of the additive with each other and to ensure the stability of the formulations during long periods of storage, even at very low temperatures.
• a solvent e) compatible with the fuel can be used hydrocarbons or mixtures thereof, such as gasolines, diesel-oil, fuel-oil, benzene, toluene, xylenes, etc.
• ethers such as methyl-tercbutyl ether (MTBE) and terc-amyl-methyl ether (TAME), ketones such as acetone, butanone, cyclohexanone, alcohols containing 6 to 18 carbon atoms such as 2-ethylhexanol, 1-dodecanol, 1-hexadecanol, isotridecilic acid, etc. and other oxygenated solvents or mixtures thereof.
• the amount of solvent to use depends on the ratio of the components a) and b) and on the nature of the component b). It is recommendable to use the minimum amount of solvent e) required to achieve the desired effect of stability during storage of the additive. Larger amounts can be used but in general are not recommendable as they dilute the active components.
• Fuels in which the additives object of the invention can be used include conventional fossil fuels derived from petroleum, such as gasolines, kerosene, diesel-oil and fuel oils.
• gasolines, kerosene, diesel-oil and fuel oils When the additives are used to improve the combustion of gasoline in internal combustion engines, other additives meant to improve the octane rating can be incorporated to the additives object of the invention, selected from among those known in the current art.
• other additives meant to improve the cetane rating can be incorporated to the additives object of the invention, selected from among those known in the current art.
• the additives object of the invention can also be advantageously used to improve the combustion of bio-diesel oils.
• the most efficient concentration of the additive in the fuel to be used depends on the specific type of liquid fuel and on the desired effect regarding the reduction of pollutants and reduction of fuel consumption and on the concentration of aminoacids in the aqueous solution a).
• the additives object of the invention are effective at levels approximately between 0.01 and 10% by weight with respect to the total weight of a) and b), and more preferably between 0.1 and 5% by weight. Any expert can easily determine the optimal levels of additive to employ in each case.
• An additive according to the invention was prepared with the following formulation:
• the additive was prepared simply by mixing the components a), b), c) at ambient temperature in a reactor with stirring for 5 minutes.
• the additive prepared according to example 1 was mixed with commercial gasoline with OR 95 in a ratio of 2 parts by volume of additive and 98 parts of gasoline.
• the test was performed with a single-cylinder internal combustion engine Mark III, with emissions control. Compression ratio 3:1, operation speed 400-4,000 rpm, power approximately 1 ⁇ 2 HP, cooling system: forced air, fuel injection system: injection by carburetor.
• a dynamometer was used to initiate and load the engine. The engine speed, couple, cylinder pressure, temperature of cooling air and engine power were determined with the dynamometer. High-accuracy calibrated rotameters were used to measure the fuel and air flows.
• Emissions of NO x , total unburned hydrocarbons and CO in the exhaust gases were measured with an in-line gas analyser connected to the exhaust pipe.
• Carbon deposits were measured gravimetrically, according to the following method: the engine was operated with a fuel-enriched air/fuel mixture, to obtain a significant formation of carbonaceous deposits on the piston after 30 minutes of operation. After each test run the engine was fully dismantled and the carbon deposited on the piston was carefully scraped and weighed with precision analytical scales. The engine was subsequently reassembled to continue the tests.
• Emissions in the exhaust gases were determined as a function of engine speed at 1500, 1750, 2000, 2250 and 2500 rpm, as well as for various equivalence ratios for the air/fuel mixture (ER defined as the actual air/fuel ratio and the stoichiometric air/fuel ratio).
• the average comparative values obtained with the 95 OR gasoline with and without additive were: reduction of up to 30% of emissions of unburned hydrocarbons (HC) and carbon monoxide (CO); increased engine power with the corresponding reduced consumption above 5%; deposition of carbon reduction by 35% when using the additivated gasoline according to the invention, compared to the amount of carbon deposited with the gasoline without the additive. This use results the shows clearly increased efficiency of combustion due to the additive object of the invention.
• Tests carried out in domestic boilers for heating and hot water supply of large numbers of joint households, hotels and hospitals using diesel oil C with 2% by volume of the additive prepared according to example 1 resulted in average fuel savings of 10-15% and a reduction in emissions of carbon monoxide of approximately 50%.
• Tests carried out in Diesel oil trucks of transportation fleets using diesel oil A with 2% by volume of the additive prepared according to example 1 provides average fuel savings of 10%, reducing emissions of smoke and soot by 35-40%, emissions of carbon monoxide by 50-75% and emissions of polynuclear hydrocarbons by 35%.

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