CS345291A3 - Cleaning additive into fuels - Google Patents

Abstract

Detergent additive for liquid fuels, obtained by means of the trans-esterification of a tertiary amine bearing at least two hydroxy functions, with a dialkyl carbonate and a higher aliphatic alcohol, and process for preparing said detergent additive.

Description

FIELD OF THE INVENTION The present invention relates to an additive for liquid propellants, in particular motor gasoline, wherein the additive is provided with cleaning properties. In addition, the present invention relates to a process for preparing such additive. use in built-in internal combustion engines operating on both Otto and Diesel cycle, while maintaining their filling systems free of deposits and impurities · Consequently, internal drilling of these components should be reduced and prevented exchanges of components for which this measure is designed and which, in the event of pollution, reduce the efficiency and energy performance ·

Background Art

For some time, certain classes of ingredients that are used alone or in blends are known as fuel additives. For example, U.S. Patent 3,676,089 refers to alkeayl succinimidypolyamines; U.S. Pat. No. 3,574,576 replaces polyamides with polyisobutylene groups; U.S. Pat. No. 3,649,229 is Polyannobutylene Phenol Base, U.S. Pat. No. 4,160,648 discloses polyoxyalkylene aminocarbonates; U.S. Pat. No. 4,193,306 to polyoxyalkylene amino esters; and U.S. Pat. ·

Such components perform their function as cleaning agents, suffering from various ranges, the drawback of the formation of carbon deposits inside the engine engine or in the combustion chambers, which cause contamination of the hot engine parts and thus do not meet the requirement of maintaining cleanliness In addition, the preparation of these components requires multiple steps of synthetic processes and very often the use of highly toxic and hazardous reactants, such as chlorine (U.S. Pat. No. 3,574,576), formaldehyde (U.S. Pat. No. 3,649,229), phosgene (U.S. Pat. No. 4,150,648) and acid (in U.S. Pat

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SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION It is a class of cleaning additives that perform the same function as both in cold engine components (ie, carburetor, pipes, injectors, inlet valves, and the like) as well as in hot engine parts (cylinders, pistons, exhaust valves, and the like). be achieved by means of a one-step easy-to-manage process in which far less is used Poisonous and dangerous reactants ·

In fact, the present invention has found that functional amine-containing carbonic esters of higher alcohols exhibit significant cleansing properties in the overall propellant composition, and in view of the substantial contamination phenomenon in hot engine parts.

Another aspect of the present invention is the process of preparing said aninocarbonates. The cleaning additive of the present invention is prepared by means of transesterification, wherein the tertiary amine has the formula R - N - Q - (O 3) n --OH 1 2 (I), wherein n is an integer from 1 to 4; R * is another - (CH 2) n --OH or alkyl radical containing 1 to 20 carbon atoms; and reacts with an organic carbonate of formula R " -O-O-R " (II), wherein R < 2 > is one C1-4 alkyl or one aryl group; - with an alcohol of the general formula R 1 -OH (III), wherein R 1 represents a pure or derived alkyl group (or a mixture of pure and derived alkyl groups) with 6 to 30 carbon atoms ·

The possible presence of etheric oxygen atoms in R 1 does not have any substantial effect on the characteristics of the resulting product in which such etheric oxygen atoms are present at a carbon ratio of at most 0.5 ·

According to a preferred embodiment of the present invention, the compound of formula (I) is triethanolamine or H-butyldiethanolamine (wherein π - 2. and wherein R * is hydroxyethyl or butyl), the compound of formula (II) is dinethyl carbonate or diphenyl carbonate. A compound of formula (III) is a linear or derived primary aliphatic alcohol having from 7 to 26 carbon atoms (obtained, for example, by oxosynthesis from linear or derived olefins and carbon monoxide, and dimerization agents for such alcohols) or a mixture of primary alcohols containing one or more the ether moieties of their alkyl chain (obtained, for example, as by-products of the condensation of alcohols in the process of oxo-synthesis alcohols from olefins and carbon monoxide) or polyoxypropylene monoeter such as polyoxypropylene monobutyl ether with a molecular weight not exceeding 10% 00.

A further object of the present invention lies in the process of preparing said aminocarbonates soluble in petroleum products which are in the liquid state. The reaction is preferably carried out in that the reactants (I), (II), (III) are brought into contact with each other in a molar ratio containing from 1: 3: 3 to 1: 10: 5, preferably 1: 5 · 3> 5 · According to the alternative form of practical composition of the process of the present invention, the final phase is divided into two steps. The first step is the reactant (I) with component (II) followed by the second step of reacting the obtained intermediate with alcohol (III). The reaction of obtaining the final product can be catalysed using transesterification catalysts (sodium hydroxide, potassium hydroxide, titanium alkaloids or derivatives). tin), but preferably dibutyltin dilaurate.

The reaction temperature ranges from 80 to 200 ° C, but at most from 100 to 180 ° C. The reaction is terminated when a certain stoichiometric amount of R 2 -OH (in the case of dimethyl carbonate or diphenyl carbonate is R ** -OH methyl alcohol or optionally phenol) was formed from the reactants. The progress of the reaction towards its termination is improved by removing the formed alcohol R * z-OH from the reactive mixture. For this reason, the reaction can be improved by azeotropic distillation of R * z-OH or by lowering the pressures, or otherwise according to circumstances well known in this mode of operation. The same reaction can also be advantageously carried out in the presence of neutral solvents such as hydrocarbons, chlorine components and the like. The result is that practically at all -OH and mostly formed as (IV) · Referring to the case of dimethyl and trigthanamine, the OCOOCH is the "+ 3 - OH -5" oar the product of the reaction contains no functional group of the compound of general alcohol use, carbonate scheme the reaction is as follows: N - (CH2 --O - OH) 3 + 3 GH3

-> N - (GH 2 - 0 - 0 - 00 - O - O -) 3 + 6 GH 3 OH C iv)

The reaction is accompanied by the appearance of a small amount of byproducts, such as the condensation products of two triethanolamine molecules with one dimethyl carbonate molecule, and

Finally, it is an object of the present invention that the propellant composition comprises a decisive portion of the liquid propellant itself and a small amount of the additive of the present invention which acts as a cleaning agent. namely the addition of this agent from 0.005 to 0.1% of the total weight · The results are sufficient for the recommended use in the range of 0.02 to 0.06% of the total weight ·

The product obtained by the transesterification according to the invention is similar to an oily fluid having a very high viscosity and would be difficult to use in this situation. For this reason, the addition of fuel to the propellant can be facilitated by using a solution with a concentration of 25 to 95% by weight ( the best from 50 to 70% ') solvent dissolved in the solvent · This solvent can be selected from suitable alcohols, esters and hydrocarbons, which have a beneficial effect on the dissolution of this product.

According to a preferred embodiment of the present invention in the form of a solution, the same type of propellant is used to add the additive, such as gasoline, kerosene gas oil. For example, at the end of the synthetic reaction the product may be diluted within the same reactor by adding a diluent in The following examples are provided for the purpose of illustrating the present invention without any limitation. Example 1: The following examples are provided for the purpose of illustrating the present invention without any limitation. 49.5 grams (0.33 moles) of 98 percent pure triethanolamine, 328 grams (1.33 moles) of G 21 ethanol (obtainable from Exxon Chemicals under the commercial designation LD-ΞΑ-21), 100 grams ( 1.1 mol) of dimethyl carbonate and 5 grains of dibutyltin dilaurate are introduced into a 1.5 l reactor The reactor is provided with a heating mantle, a rotating blade mixer, a thermoelectric cell connected to a thermometer, a dropping funnel, and a 10 cm long distillation column, which is coupled to a Claisen thermometer condenser system. at about 115 ° C, which is achieved by circulating a heating solution coming from a temperature-controlled bath inside the reactor shell · An inert nitrogen atmosphere is maintained inside the reactor · The reaction proceeds by developing a methanol which is distilled off in the form of which it is formed · In fact, however, an azeotropic mixture of dimethyl carbonate and methanol in the composition of about 1: 1 is produced. The development of this mixture is controlled by maintaining the main temperature below 65 ° C. During the course of the reaction, the dimethyl carbonate remaining in the azeotrope mixture is replaced by the addition of approx. 65 grams of this material through the dropping funnel, wherein said dimethyl carbonate is always kept lighter in the reactive mixture. After two hours, the main temperature is gradually raised to 185 ° C for four hours. This temperature value is then maintained for a further 10 hours. 110 grams of azeotropic mixture is obtained, the reaction progress is controlled by "IR" analysis of the hydroxyl group · This operation is completed after about 16 hours when the hydroxyl number drops to about 10 milligrams KOH / g · Then the reacting mixture is purged with a nitrogen stream this operation is carried out at a temperature close to 185 ° C and a flow rate of nitrogen of 100 cc per minute for one hour. The reaction product, which may be referred to herein as "Additive A", is a light yellow liquid having the following characteristics:

Obsan dUSUXU

Hydroxyl number (ASTM D 1957) Τ · Β · Η · (total base number) (ASTM D 664)

Pour Point (ASTM D 97)

Visco rye at 100 ° C (ASTM D 445) Viscosity at 40 ° G (ASTM D 445)

Thermogravimetric analysis performed on a Perkin Slmer TGA7 weighing a 1.2 milligram sample which is heated to 50 ° C to 500 ° C at a temperature of 10 ° C per minute and a nitrogen flow of 25 cc per minute: 42.75 mg Wg : - 45 ° 0: 11 cSt: 90.8 cS t

: 100% loss is recorded at 35O ° C Example # 49.5 grams of triethanolamine (0.333 mol), 200 grams (1.0 mol) of isotridecile alcohol (a commonly derived alcohol obtained by oxidation from propylene tetramers manufactured by Henkel), 100 grams (1.1 mol) of dimethyl carbonate and 3.9 grams of dibutyltin dilaurate are incorporated into the previously described reactor.

The reaction mixture is heated to 115 ° C and an additional 65 grams of dimethyl carbonate is added through a dropping funnel. After an hour, the temperature is gradually raised to 180 ° C over the next 8 hours. to reach 110 grams of azeotropic mixture, the reaction begins to be controlled by " I · R " by analyzing the crude reaction mixture. This operation is completed after about 16 hours when the hydroxyl number drops to about 8 milligrams of KOH / g. with the help of the nitrogen-free expulsion of the crude mixture, which is the result of the reaction (180 ° Cza for 1 hour with a flow of nitrogen of 100 cc per minute) · The reaction which can be referred to herein as "Additive B" is a light yellow liquid having the following characteristics:

Nitrogen contentHydroxyl number T.B.N.

Freezing point 1,54% weight7,7 mg KOH / g61 mg KOiV g- 51 ° C6,62 cSt40,35 cSt

100% loss at 335 ° C (ASTM D 1957) (ASTM D 664) (ASTM D 97) (ASTM D 445) Viscosity at 40 ° C (ASTM D 445)

Thermogravimetric analysis (similarly as in Example 1)

Viscosity at 100 G G0ž has the following characteristic 2,299 liters95,5 mm80,25 mm100 kU205 Nm Example # 3 ·

The effectiveness of the thus-discovered components and their mixtures while maintaining the purity of the injection nozzles of the internal combustion engine was evaluated by means of appropriate engine testing, in particular 3 using the Mercedes M 102 3 engine:

Contents / Litter DrillingTrack

Maximum power at 5,100 rpmMaximum torque at 3,500 rpm

The test duration is 60 hours and the engine running conditions are determined by the “Injector Cleaning Test Test”, an official procedure of F3V approved in September 1988 · Unleaded petrol marked '' Eurosuper '', which contains 3, was used in the test 86% methyl tert-butyl ether (MTBE) as an anti-concrete additive and delivered 400 parts by volume of "Additive A" per million by volume of propellant. This additive has been developed according to "Example 1". : (ASTM L 1298) 0.749 kg / liter 96.3 86.3 36% 5% content 59% 2 mg / 100 ccla (ASTM L 1319) (ASTM D 1319)

Specific gravity at 15 ° CROM (ASTM D 2699) MON (ASTM D 2700) FIA: aromatic olefins saturated hydrocarbons (ASTM D 1319) Useful resins (ASTM L 381)

Copper corrosion (ASTM D 130) Four injection nozzles were weighed before and after the test · The difference in weight, expressed in milligrams, shows the amount of sediment formed during the test · The occurrence of deposits is further evaluated by assisting methods when compared to standard nozzles. The results are readable on a value scale from 1 to 10 in accordance with the "CRC Handbook 5" (Value Level 10 stands for pure engine). The test results obtained with the use of "Additive A" gasoline and verified by comparing the average of two test runs were Average weight of deposits: 108 mg

Value stage: 8.96-Í-- »» C5 Λ ay, e, 3, 3uu preparation py ± n 3 U U v v v v v v 1 "" "ot ot ot ot systému systému systému systému ( the carburetor nozzles and parts) was also defined by the engine test means in the case of the Opel Kadet 1.2 S engine. The procedure prescribed by the "Coordinating European Oouncil", F - 04 - A - 37 · On the one hand, the original gasoline, the characteristics of which were previously described, and on the other hand gasoline, which contained 400 parts by volume of the "Ingredients and produced according to the description of the procedure" example, were used * Example δ · 1 '' · The test was carried out when filling the engine with two independent carburetor systems, so that the two cylinders burned the original gasoline and the two remaining cylinders burned gasoline with the specified additive, tested in this way. of the valves, the ratios of the carburettors depending on the pair of gasoline burners without the additive, and to the pair of gasoline burners with admixed additive, it was possible to evaluate the effectiveness of the test additive.

Injection Nozzle Pollution 413 mg 214 mg Purity Value (SHČ) (Injector Nozzle) 6.70 7.90SHF (Shut-off Valve Body) 9.22 9.96SHF (Injection Pipe) 8,30 8,90SHF (Shut-off Valve) 9 26 9.46

The use of the discussed additive reduces the weight of deposits on the injection nozzles by 48.2% compared to the effects of gasoline containing this additive. In addition, the purity grades on the carburetor components are higher in the case of gasoline with this additive.

INDUSTRIAL APPLICABILITY The additive according to the present invention, both in concentrated form and in other formulations, is compatible with other additives which are jointly useful for improving the properties of fuels or propellants of the incinerator, such as anti-knock additives, emulsion and foam removers, dispersants, corrosion prevention agents, etc. ·

Claims (6)

'MSI -Ή i. 1) Cleaning additive for fuels and propellants of built-in combustion engines, characterized in that it is prepared by means of transesterification (I) of tertiary amine formula R * - N - C - ( Wherein R is an additional scale number of from 1 to 4 and R is another - (C 1-6) n OH or alkyl radical containing from 1 to 20 carbon atoms; (II) an organic carbonate having the formula R 10 -O-CO-O-R 1 wherein R 1 is an alkyl group having from 1 to 4 carbon atoms or is an aryl group; (III) an alcohol having the formula R 1 -OH, wherein R 1 represents a pure or derived alkyl group (or a mixture of direct or derived alkyl groups) having from 6 to 30 carbon atoms; 2. A liquid propellant cleaning agent according to claim 1, wherein component (III) is a alcohol with a ratio of ethereal oxygen atoms to carbon atoms greater than 0.5. A liquid propellant cleaning agent according to one or more of claims 1 to 2, wherein component (I) is triethanolamine or N-butyldiethanolamine (n = 2a R * is hydroxyethyl or butyl); component (II) is carbonate-dimethyl or diphenyl carbonate; component (III) is a mixture of linear or derived primary aliphatic alcohols containing one or more etheric groups in their alkyl chain, or polyoxypropylene glycol monobutyl ether; The process for preparing a liquid propellant cleaning agent according to one or more of 1 to 3, characterized in that the reaction is carried out at 80-200 ° C, but at 100-180 ° C, using a molar ratio of reactants ( (I), (II), (III) containing a range of 1: 3 and 3 to 1: 10: 5> the best ratio is 1: 5: 3) in the presence of transesterification catalysts, of which the most suitable is dibutyltin dilaurate · 10 Liquid propellant cleaning additive concentrate, characterized in that it comprises an amount of the product according to one or more points from 1 to 3 comparable with a range of 25 to 95% by weight, most preferably 50 to 70%. 6 · Liquid propellant composition for built-in combustion engines, characterized. characterized in that it comprises an additive of one or more of 1 to 3 in an amount comparable to 0.01 to 0.1% by weight, most preferably 0.02 to 0.06% by weight.