Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a process for preparing an additive for liquid fuels, in particular gasolines, which additive is endowed with detergent properties.
• Such compounds perform their task as detergents, but suffer -- to various extents -- from the drawback that they, inside the engine ignition or combustion chambers, create carbonaceous deposits, which result to be fouling for the hot engine parts, and do not meet the requirement of keeping clean also such parts.
• the subject-matter of the present invention is a process for preparing a class of detergent additives which fulfil such a function both in cold engine parts (i.e., the carburettor, conduits, injectors, intake valves, and so forth), and in hot engine parts (cylinders, pistons, exhaust valves, and so forth), said process being a single-step process easy to be practiced, by starting from reactants which are by far less toxic and dangerous.
• the present Applicant found that the carbonic esters of higher alcohols containing a functional amino group display marked detergent properties in fuel compositions, without substantial phenomena of fouling in the hot engine parts.
• the present invention concerns a Process for preparing a detergent fuel additive which comprises the step of transesterifying
• R3 of possible ethereal oxygen atoms does not have any substantial effects on the characteristics of the resulting product, provided that such ethereal oxygen atoms are contained within a ratio of ethereal oxygen atoms to carbon atoms of 0.5 max.
• the reaction is preferably carried out by bringing (I)/(II)/(III) reactants into contact with one another, in a mutual molar ratio comprised within the range of from 1:3:3 to 1:10:5, preferably in ratios of round 1:5:3.5.
• the latter is subdivided into two steps: i.e., a first reaction of (I) with the excess of (II), and a subsequent reaction of the intermediate obtained in that way, with alcohol (III).
• the reaction leading to the product of the present invention can be catalysed by the usual trans-esterification catalysts (sodium hydroxide, potassium hydroxide, titanium alkoxides or tin derivatives), preferably dibutyltin dilaurate.
• trans-esterification catalysts sodium hydroxide, potassium hydroxide, titanium alkoxides or tin derivatives
• the reaction temperature is comprised within the range of from 80 to 200°C, preferably of from 100 to 180°C.
• the reaction is complete when the stoichiometric amount of R"-OH (in the case of dimethyl carbonate or diphenyl carbonate, R"-OH is methanol, or phenol, respectively) was formed from the reactants.
• the reaction development towards its completion is favoured by subtracting from the reaction mixture the alcohol R"-OH which is formed.
• the reaction can be favoured by azeotropically distilling off R"-OH, or with reduced pressures, and so forth, according to modalities well known in the art.
• the same reaction can be advantageously carried out as well in the presence of inert solvents, such as hydrocarbons, chlorinated compounds, and so forth.
• the raw reaction product results to be practically free from functional -OH groups, and is prevailingly constituted by the compound of general formula (IV).
• the reaction scheme is as follows: N-(CH2-CH2-OH)3 + 3 CH3OCOOCH3 + 3 C12-OH ⁇ ⁇ N-(CH2-CH2-O-CO-O-C12)3 + 6 CH3OH
• reaction is accompanied by the appearance of minor amounts of reaction byproducts, e.g., of condensation products of two molecules of triethanolamine with one molecule of dimethyl carbonate, and so on.
• the additive according to the present invention results to be effective as a detergent already in very small amounts; the addition of from 0.005 to 0.1% by weight, preferably of from 0.02 to 0.06% by weight, results to be sufficient.
• the product obtained from the trans-esterification according to the present invention is an oil-like liquid, having a considerably high viscosity, and difficult to be handled. Due to this reason, the addition thereof to the fuels can be made easier if it is used as a solution, e.g., as a concentrate containing from 25 to 95% by weight, and preferably from 50 to 70%, of the additive, dissolved in a solvent.
• the solvent can be selected from among alcohols, esters, ethers, hydrocarbons acting as good solvents for the product.
• the same type of fuel can be used as the solvent, to which the additive will be subsequently added, such as, e.g., gasoline, gas oil, kerosene.
• the product is diluted, inside the same reactor, by adding to it the diluent, in the desired amount, and using the same stirring means.
• the additive obtained according to the process of present invention is compatible with the other additives which are commonly used for combustibles or fuels for internal combustion engines, such as, e.g., antiknock, de-emulsifier, dispersant, antifoaming, rust-preventing additives, as normally used.
• additives which are commonly used for combustibles or fuels for internal combustion engines, such as, e.g., antiknock, de-emulsifier, dispersant, antifoaming, rust-preventing additives, as normally used.
• the temperature inside the reaction vessel is increased up to approximately 115°C, by causing a heating fluid coming from a temperature-controlled bath, to circulate inside the reactor jacket. Inside the reactor, an inert atmosphere of nitrogen is maintained.
• the reaction proceeds with development of methanol, which is distilled off as it is formed: in fact, an azeotropic mixture of dimethyl carbonate/methanol with a composition of about 1:1, is formed. Its development is controlled by maintaining the head temperature under 65°C.
• dimethyl carbonate lost through the azeotropic mixture is replenished by adding approximately 65 g thereof through the dripping funnel, with said dimethyl carbonate being hence kept always in a slight excess in the reaction mixture.
• the head temperature is gradually increased during 4 hours, until it reaches the value of 185°C.
• This temperature value is then maintained for a further 10 hours and, after collecting 110 g of azeotropic mixture, the course of the reaction is started to be checked by I.R. analysis for the hydroxy group.
• the operation is completed, after about 16 hours, when the hydroxy number decreases down to values of about 10 mg of KOH/g.
• the reaction mixture is then purged with a nitrogen stream, by operating at the temperature of about 185°C and with a nitrogen flow rate of 100 cc/minute, for one hour.
• the reaction product hereinafter indicated to as "Additive A" is a pale yellow liquid having the following characteristics:
• the reaction mixture is heated up to 115°C, and through the dripping funnel, a further 65 grams of dimethyl carbonate is added. Two hours later, the temperature is gradually increased, within an 8-hour period, up to 180°C. This temperature is maintained for a further 6 hours and, after collecting 110 grams of azeotropic mixture, the reaction course begins to be checked by means of the I.R. analysis of the raw reaction mixture. The operation is ended, after about 16 hours, when the hydroxy number decreases down to values of about 8 mg of KOH/g. Then, a mild stripping, with nitrogen, of the raw reaction mixture is started (180°C for 1 hour, with a nitrogen flow rate of 100 cc/minute).
• the reaction product hereinafter indicated to as "Additive B" is a pale yellow liquid, which has the following characteristics:
• the test time is of 60 hours, and the engine operating conditions are provided for by the "Intake Valve Cleanliness Test” method (FEV- Procedure, September 1988).
• An unleaded Eurosuper gasoline was used, containing 3.86% of methyl-tert.butyl-ether (MTBE), as anti-knock additive, and to which 400 parts by volume per million parts by volume (ppm vol/vol) of Additive A, produced as disclosed in Example N. 1, had been added.
• MTBE methyl-tert.butyl-ether
• the four intake valves of the engine were weighed before, and after the test.
• the difference in weight expressed as milligrams, is indicative of the amount of deposits formed during the test.
• the appearance of the deposits is furthermore evaluated by means of a visual method, by comparison to standard valves.
• the evaluation is given as a merit rating from 1 to 10, according to the method of CRC Manual N. 5 (a merit rating 10 indicates a completely clean engine).
• the test is carried out by feeding, through a system of independent carburettors, two cylinders with the gasoline without additive, and both residual cylinders with the same gasoline, containing the additive under test.
• the comparison of the results (valve fouling, carburettor merit ratings), relevant to the pair of cylinders fed with additive-free gasoline and to the pair of cylinders fed with gasoline with additive added, makes it possible the effectiveness of the tested additive to be evaluated.
• Test results were the following: Gasoline in pristine state Gasoline with additive added - Intake valve fouling (mg) 413 214 - Cleanliness merit rating (intake valves) 6.70 7.90 - Cleanliness merit rating (throttle valve body) 9.22 9.96 - Cleanliness merit rating (intake manifold) 8.30 8.90 - Cleanliness merit rating (throttle valve) 9.26 9.46

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Detergent Compositions (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)
• Liquid Carbonaceous Fuels (AREA)

Applications Claiming Priority (2)

Publications (2)

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Family Applications (1)

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• 1990
  • 1990-11-15 IT IT02207290A patent/IT1245738B/it active IP Right Grant
• 1991
  • 1991-11-08 AT AT91202897T patent/ATE134699T1/de not_active IP Right Cessation
  • 1991-11-08 ES ES91202897T patent/ES2084092T3/es not_active Expired - Lifetime
  • 1991-11-08 DE DE69117442T patent/DE69117442T2/de not_active Expired - Fee Related
  • 1991-11-08 EP EP91202897A patent/EP0486097B1/en not_active Expired - Lifetime
  • 1991-11-08 SG SG1996000656A patent/SG54114A1/en unknown
  • 1991-11-08 DK DK91202897.4T patent/DK0486097T3/da active
  • 1991-11-14 CZ CS913452A patent/CZ282836B6/cs unknown
  • 1991-11-14 CA CA002055573A patent/CA2055573A1/en not_active Abandoned
  • 1991-11-14 HU HU913575A patent/HU210794B/hu not_active IP Right Cessation
  • 1991-11-14 RU SU915010309A patent/RU2036954C1/ru active
  • 1991-11-14 KR KR1019910020218A patent/KR940008390B1/ko not_active Expired - Fee Related
  • 1991-11-14 MX MX9102064A patent/MX173928B/es not_active IP Right Cessation
  • 1991-11-14 BR BR919104962A patent/BR9104962A/pt not_active Application Discontinuation
  • 1991-11-15 PL PL91292412A patent/PL167977B1/pl unknown
  • 1991-11-15 JP JP3327078A patent/JPH04292690A/ja not_active Withdrawn
• 1996
  • 1996-03-12 GR GR960400663T patent/GR3019262T3/el unknown

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