MXPA00007248A - Solid fuel additive - Google Patents

Abstract

The invention relates to solid or pasty fuel additive compositions produced from a homogenous mixture of a solid solidifying agent which is soluble in fuel, and at least one liquid fuel additive, whereby the compositions comprise an additive content of more than approximately 40 to approximately 99 wt.%with regard to their total weight.

Description

"SOLID ADDITIVES FOR COMBUSTIBLE" The present invention relates to solid or pasty additive compositions for fuels. Carburetors and intake systems -of gasoline engines as well as injection systems for fuel dosing in gasoline and diesel engines are being contaminated considerably by impurities. The impurities are caused by particles of air dust sucked through the engine, unburned hydrocarbon residues from the combustion chamber and crankcase ventilation gases that have passed into the carburetor. This waste displaces the air / fuel ratio during idling and the bottom load scale so that the mixture is richer and the combustion more incomplete. As a result, the proportion of unburned or partially burned hydrocarbons in the exhaust gas, and increases gasoline consumption. It is known that fuel additives for maintaining valves and carburetor or injection-clean systems are used to avoid -these disadvantages (see for example: M. Rossenbeck in Katalysatoren, Tenside, Mineraloladditive, Editors J. Falbe and U. Hasserodt , page 223, G. Thieme Verlag, Sttugart 1978). Depending on the mode of action and the preferred place of action of these detergent additives, a distinction is now made between two generations of additives. The first generation of additives will only be able to prevent the formation of deposits in the admission system, but not to remove existing deposits. On the other hand, additives from the second generation prevent and eliminate deposits. They exhibit both an effect of staying clean and a cleaning effect. This is allowed, in particular by its excellent heat stability in relatively high temperature zones, in particular in the intake valves. These detergents, which can originate from many kinds of chemical substances, are generally used in combination with carrier oils and, if required, additional additive components, for example, corrosion inhibitors and demulsifiers. These formulations of the liquid additive are added as a rule by means of dosing apparatuses appropriate to the fuel, where they present their action. However, in the storage and distribution of fuels, there are also cases where an appropriate dosing facility for liquid fuel additives is not available. Here, the existence of fuel additives in solid form, which dissolve in fuels would be useful and advantageous. They would constitute a considerable improvement compared to liquid additives, since the technical complexity and the high cost of a dosing apparatus would be avoided. The Patent Number DE-A-44 31 409 discloses an additive paste of pumpable fuel that can be dosed directly to the fuel feed line. The paste has an additive content of about 5 percent to 35 percent by weight and containing from 10 percent to 60 percent by weight of oils, fats and / or waxes and from 1 percent to 10 percent by weight of a thickener, vg bentonite. A disadvantage of these fuel additive formulations is the poor handling properties of the pasty product and the high technical complexity for dosing the pulp to the fuel. Patent Number CA-A-2 143 140 discloses solid additives for internal combustion engines. The solid formulation is prepared by absorbing a liquid additive in a porous carrier, soluble in the solid fuel, preferably a carrier based on naphthalene, and closing the pores of the carrier after adsorption of the additive. A disadvantage of these solid additives is their inconvenient preparation process. A further serious disadvantage is the limited adsorption capacity of the naphthalene granules used. For example, it is stated that a 1.6 gram granule can typically absorb only an amount of additive corresponding to one third of its volume. U.S. Patent Number A-4 639 255 discloses several compositions of solid additive for fuel. According to a first embodiment described herein, a granular additive formulation having an additive content of from about 25 percent to about 75 percent by weight, based on the weight of the composition, is provided of course. The additive is contained in a consolidation agent dispersible in the fuel, for example, paraffin wax, and the granules of the additive are sealed on its surface. Examples of preferred additives are hydrogenated polybutenes having a molecular weight of from about 700 to about 1100 and the reaction products of one or more vegetable oils and a polyethyleneimine further derived with a sulfonic acid. US Patent Number A-4 639 255 further describes the formulations of the solid fuel additive which contains, as a consolidating agent, an aromatic hydrocarbon, for example, naphthalene or the easy sublimation durene (1,2,4,5- - tetramethylbenzene) in an amount of about 50 percent to 95 percent by weight. An additional solid additive formulation contains, in addition to the consolidating agent, a long chain alcohol as a modifier to increase the melting temperature. Another solid additive formulation has an additive content of 5 percent to 40 percent by weight, the granules of the additive having a coating of foamed paraffin wax. Finally, U.S. Patent Number A-4 639 255 describes an additive formulation having a foamed carrier. All of the solid additive formulations described above are still not completely satisfactory with respect to their additive content and / or because of their relatively complicated preparation. U.S. Patent No. A-4 639 255 expressly states to those skilled in the art and the content of the additive in the uncoated formulation can be no greater than 40 weight percent, and preferably should be about 10 percent by weight. 30 percent, in particular from approximately 15 percent to 25 percent by weight. An object of the present invention is to provide solid and pasty fuel additive formulations that are distinguished both by a high content of additive and by simple preparation. In - In particular, it is intended to provide highly concentrated detergent, solid or pasty additive formulations. We have found that this object is achieved, surprisingly by providing an additive composition for fuel which is non-fluid, solid or pasty under normal conditions of temperature and pressure, which can be used in particular in gasoline fuels, and which comprises a mixture, preferably homogeneous of a solid, soluble or dispersible agent in the fuel, and at least one liquid fuel additive, the composition having an additive content of more than 40 percent to about 99 percent, preferably of about 50 percent at 95 percent, for example, from about 60 percent to 90 percent by weight, or from about 75 percent to 90 percent by weight, based on your total weight. The novel additive compositions have the advantage that, due to their high additive content, they have considerably improved performance. In addition, they have the advantage that they can be prepared by simply incorporating the additive or additives in for example, a melting of the consolidating agent that is solid at room temperature, homogenizing the mixture, if required allowing it to cool and making it in an appropriate manner. It is not necessary to foam the consolidating agent or subject the solid formulation, for example, processed to provide granules, to no surface treatment. The novel formulations also have the advantage that they can be added to the fuel without a pump apparatus. In addition, the dosage can be adjusted more easily and the viscosity requirements of the product containing the additive are easier to satisfy. Statements of aggregation status, such as solid, liquid or pasty, are made in the context of the present disclosure with reference to normal temperature and pressure conditions, i.e., approximately 20 ° C and approximately 1 pressure. atmosphere. A novel solid or pasty composition has a melting scale or a melting temperature of about 25 ° C to 95 ° C, preferably about 30 ° C to 90 ° C, in particular, about 35 ° C to 70 ° C. , for example, from approximately 35 ° C to 50 ° C. Expressing differently, the contents of the additive mentioned in the context of the present invention are the sum of the contents of all the components for the respective formulation other than the consolidating agent.

A homogeneous composition is present if they are not visually detectable in the novel solid, phase limits or separation regions. In a preferred embodiment, the novel compositions contain at least one detergent additive as the main additive component. In particular, the additives that both prevent the formation of deposits in the intake valves and eliminate the deposits already formed, are of course used. Therefore, they exhibit both a clean keeping effect and a cleaning effect. Suitable additives according to the invention are selected from polyetherramides, for example, poly-C2-Ce-alkylenoxy amines and polyalkenamines, such as poly-C2-C6-alkenamines, and functional derivatives thereof. Particularly preferred detergent additives are selected from the polyisobutene amines and functional derivatives thereof. The polyisobutene part of these additives can be prepared, for example, from a C4 distillation fraction which is usually obtained from thermal or catalytic disintegration and which has a high isobutene content, by means of e.g. cationic polymerization. The polyisobutene part can also be derived from mixtures of n-butene and i-butene, e.g. by cationic polymerization, wherein the molar ratio of n-butene and of i-butene can be freely selected, and for example, can be freely adjusted within the range of 1:20 to 20: 1, e.g. from 1:10 to 10: 1. The polyisobutene part can also be derived from i-butene, essentially pure, e.g. by cationic polymerization and, therefore, contains approximately 100 percent of i-butene units in polymerized form. Preferably, the aforementioned polyalkyleamines are prepared from the so-called reactive polyalkene which is known from the prior art. This preferably has a high content of terminal double bonds, e.g. of about >; 50 percent or _ > 70 percent or > . 90 percent. According to the invention, a functional derivative is understood as meaning chemically modified detergent additives, which have a cleaning effect that is qualitatively comparable, but not necessarily completely identical at the level or intensity of that of a detergent additive. The detergent additives preferably used according to the invention are known per se from the prior art. Polyisobutenemines are described, for example, in Patent Numbers EP-A-0 244 616 and EP-A-0 578 323. Additional detergent additives suitable in accordance with the invention are described, for example, in the European Patent Applications Numbers EP-A-0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810 and 0 568 873; in German Patent Applications Numbers DE-A-39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 0 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06, 844, 196 16 569, 196 18 270 and 196 14 349; and in O-A-96/03479. The particularly useful liquid detergent additives are sold by BASF AG, Ludwigshafen under the factory name Kerocom® PIBA. These contain polyisobutenemines dissolved in aliphatic hydrocarbons of C14-14 carbon atoms. The detergent additives used in accordance with the invention, in particular, the polyisobutenamine additives preferably used, usually have a number-average molecular weight Mn of from about 150 to about 5000, preferably from about 500 to about 2000, in particular from about 800 to 1500 grams per mole. The content of the detergent additive, for example, polyisobutene amines and functional derivatives thereof, is from about 20 percent to 100 percent, preferably more than 30 percent, particularly more than 40 percent by weight, for example , from about 45 percent to 70 percent by weight, based on the total weight of the additives contained in the novel composition. If the detergent additive component is present in this amount, the term main additive component of the composition is used in the context of the present invention. The amount of the detergent additive for example may be more than about 10 weight percent, for example from 15 weight percent to 30 weight percent or more, such as from about 40 weight percent to 99 weight percent or 50 weight percent. percent to 95 percent by weight, or from 60 percent to 90 percent by weight from 75 percent to 90 percent by weight, based on the total weight of the solid or pasty additive formulation. In addition to the detergent additive, conventional, additional fuel additives and other additives may be present, for example, corrosion inhibitors, demulsifiers and dyes. If necessary, carrier oils can also be added. Examples of usable carrier oils or carrier liquids are mineral carrier oils, synthetic carrier oils and mixtures thereof which are compatible with the additive or additives used and the fuel. Suitable mineral carrier oils are fractions obtained in the processing of mineral oil, such as kerosene or naphtha, Brightstock oils or minerals having a viscosity of SN 500-900 as well as aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.

Examples of suitable synthetic carrier oils are polyolefins (poly) esters, (poly) alkoxylates and in particular, aliphatic polyethers, aliphatic polyetheramines, polyethers initiated with alkylphenol and polyetheramines initiated with alkylphenol. Suitable carrier oil systems are described, for example, in Patent Numbers DE-A-38 38 918, DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074 Patent North American Number A-4 877 416 and EP-A-0 452 328, which are expressly incorporated herein by reference.

Examples of suitable carrier oils, particularly are alcohol initiated polyethers having from about 15 to 30, for example, from about 20 to 25 alkylene oxide units of 3 to 6 carbon atoms, for example, which are selected from units of propylene oxide, n-buylene oxide and isobutylene oxide or mixtures thereof. A typical additive mixture contained in a novel composition comprises, for example: a) from about 20 percent to 80 percent, preferably from about 60 to 80 percent by weight of at least one polyisobutenamine or a functional derivative thereof , b) from about 20 percent to 80 percent, preferably from about 20 percent to 40 percent by weight of at least one synthetic carrier liquid, for example a polymer initiated with alkylphenol, for example about 15 percent compound. at 30, for example from about 20 to 25 alkylene oxide units of 3 to 6 carbon atoms, for example propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, and / or at least one carrier oil based on mineral oil, and c) from 0 percent to about 5 percent, preferably from about 1 percent to 4 percent by weight of at least one additive ad In addition to the aforementioned type, but differing from a), the stated weights are based on the total weight of components a), b) and c) added to the consolidating agent. Suitable additive mixtures have, for example, a boiling temperature of more than 120 ° C, for example of more than 150 ° C or 180 ° C, a density (15 ° C, DIN 51757) of "about 0.8 to 0.9 gram. per cubic centimeter and a viscosity (20 ° C, DIN 51562) of about 50 to 200, for example about 70 to 160 square millimeters per second These additive blends can be obtained as commercial products, for example under the trade name Keropur® 3222, 3131 and ES 3401. The consolidating agent used for the preparation of novel additives is preferably soluble in the fuel and usually has a melting temperature or softening temperature above the corresponding values of the composition prepared, example, from about 30 ° C to 100 ° C, preferably from about 30 ° C to 90 ° C, in particular from 40 ° C to 70 ° C. In particular, the consolidating agent is selected from (a) waxes natural, soluble in the fuel, for example petrochemical waxes, in particular paraffin wax and gasoline; (b) chemically modified waxes, for example hard waxes and (c) synthetic waxes, for example high molecular weight polyethylene wax and polyisobutene (see, for example, Ullmann's Encyclopédie der der Technischen Chemie, third edition, volume 18, page 262 and following). Some examples of suitable fuel soluble waxes are also disclosed in U.S. Patent Number A-4 639 255. The aforementioned publications are expressly incorporated herein by reference. Mixtures of the aforementioned consolidating agents can also be used.

- Suitable consolidating agents according to the invention have a solubility in fuel of up to about 10 percent based on the weight of the fuel used. The novel fuel additive compositions can be prepared in a simple manner using commonly known methods. For this object, the consolidating agent is preferably heated to its softening temperature, the fuel additive or the additive mixtures and, if the carrier oil is required, added while stirring and stirring is continued until a homogeneous mixture. The liquid mixture is then allowed to solidify. It is also possible to incorporate the additive into the consolidating agent by whipping or by melt extrusion. The prepared composition is then manufactured by extrusion or granulation. It is also possible to provide the composition in the form of a pill or powder. The encapsulation of granules or pills is possible, but not necessary. The novel additive compositions can be added to the fuel without specific technical apparatus, for example directly after being loaded into the tank truck. The metered units, for example, the granules are added in an amount required to establish a detergent additive concentration of about 20 to 5000, for example about 400 to 900 milligrams per kilogram of fuel. The examples that will be given below illustrate the invention. Unless otherwise stated, the determination of the density is carried out in accordance with DIN 51757 and the determination of viscosity in accordance with DIN 51562.

Example 1: Preparation of a solid additive composition a) 100 grams of a conventional additive composition for gasoline fuel (Keropur® 3222) (boiling temperature:> 165 ° C, density (15 ° C) = 0.865 gr / ml, viscosity (20 ° C) = 120 mm2 / s, 25 weight percent polyisobutenamine, Mn = 1000, as detergent) are mixed with half the amount of a commercial hard melted paraffin (melting temperature = 55 ° C) while stirring. After homogenization of the mixture, it is allowed to cool to room temperature, the paraffin solidifying again and the additive remaining encapsulated. The solid fuel additive prepared in this way is soluble in conventional fuels. b) Example la) was repeated, but the additive and hard paraffin were used in a ratio of 1: 1. An additive composition is also obtained for solid fuel soluble in the fuel.

Example 2: Preparation of a solid additive composition 80 grams of the polyisobutenamine (Mn = 1000) were kneaded with the same amount of hard paraffin (melting temperature = 55 ° C) in a beater (200 milliliter beater of Werner and Pfleiderer) for one hour at 20 ° C. After this processing step, the detergent is present in solid form (melting scale from 35 ° C to 40 ° C).

Example 3: Determination of the cleaning effect of a solid additive formulation The novel solid fuel additives were tested, in particular with respect to their suitability as cleaners for the intake valve, with the aid of engine tests which are carried out in tests of the test bed with an Opel Kadett engine in accordance with CEC F-04-A-87. The additive prepared according to Example Ib) was added to the commercial gasoline fuel in an amount corresponding to an amount of 600 milligrams of Keropur / kilogram of the fuel. The results are summarized in Table 1, which is presented below.

Table 1 Additive Dose Valve tanks [mg / kg] intake [mg / valve] 4 Basic value 510 277 250 467 Fuel additive 1200 45 of solid gasoline according to Ex. Ib) The results of the test show that the intake valve deposits were reduced considerably compared to the basic value in the absence of additives.

Examples 4 to 8 Additional novel additive formulations were prepared on the basis of the experimental method of Example 1 and tested for melting behavior, fuel solubility and bleed. The determined experimental results are summarized in Table 2. The experimental results determined show that the stable highly concentrated novel additive formulations can be prepared in a simple manner from liquid fuel additives. Table 2 Additive Mixing ratio PIBA7 'Consistency Scale of additive: paraffin5' [% by weight] [at 20 ° C] melt [° C] Keropur "2: 1 16.5 solid 35-40 ES 3401i) 4: 1 20 pasty 35-40 Keropur® 2: 1 15.5 solid 35-40 3222 4: 1 20 pasty 35-40 Keropur "2: 1 16.5 solid 35-40 3131 3) 4: 1 20 pasty 35-40 Table 2 (Continued) Additive Bleed 6) Solubility '4) Example [at 20 ° C] [Weight%] No.

Keropur "10 Keropur "not 10 the Keropur * no 10 31311 'not 10 1) liquid gasoline fuel additive containing 25 weight percent PIBA (Mn = 1000) in a mineral carrier oil composition boiling temperature > 150 ° C density (15 ° C) = 0.86 grams / cubic centimeter viscosity (20 ° C) = 160 square millimeters / second 2) liquid gasoline fuel additive containing 25 percent by weight of PIBA (Mn = 1000) in carrier oil composition, comprising a mixture of mineral carrier oil and a synthetic polyether carrier oil) liquid gasoline fuel additive containing 25 weight percent PIBA (Mn = 1000) in a mixture of carrier oils based on synthetic polyether; Boiling temperature > 180 ° C density (20 ° C) = 0.87 gram / cubic centimeter viscosity (20 ° C) = 70 square millimeters / second) was determined in gasoline fuel at 20 ° C) commercial hard paraffin; melting temperature = 55 ° C) was visually determined) polyisobutyleneamine, Mn = 1000

Claims (3)

R E I V I N E I C C O N E S

1. A fuel additive composition comprising a homogeneous mixture of a solid fuel-soluble consolidating agent and at least one liquid fuel additive, the composition has an additive content of more than about 40 percent to about 90 percent by weight, based on its total weight, being solid or pasty under normal conditions of temperature and pressure, and containing at least one detergent additive in an amount of more than about 10 weight percent based on the total weight of the composition .

2. A composition according to claim 1, which is melted within the range of about 25 ° C to 95 ° C.

3. A composition according to claim 1, wherein the detergent additive is selected from polyetheramines and polyalkenamines, in particular from polyisobutenes, and functional derivatives thereof. . A composition according to claim 3, wherein the content of the detergent additive is from about 20 percent to 100 percent by weight, based on the total weight of the additives contained in the composition. A composition according to claim 4, which contains at least one additional additive, which is selected from corrosion inhibitors, demulsifiers and dyes and, if required, at least one carrier oil. 6. A composition according to any of the preceding claims, wherein the consolidating agent has a melting temperature of about 30 ° C to 100 ° C. A composition according to claim 6, wherein the consolidating agent is selected from natural fuel soluble waxes, chemically modified waxes and synthetic waxes, in particular, paraffin wax, polyethylene wax, high molecular weight polyisobutene and Vaseline and mixtures thereof. 8. A composition according to any of the preceding claims, which contains an additive mixture comprising approximately a) from 20 percent to 80 percent by weight of at least one polyisobutenamine, b) from 20 percent to 80 percent weight percent of at least one synthetic carrier liquid or carrier oil based on mineral oil, and c) from 0 percent to 5 percent by weight of at least one additional additive, the contents stated each is based on the total weight of components a), b) and c), added to the consolidation agent. A composition according to any of the preceding claims, which contains at least one polyisobutenamine having an Mn of about 150 to 5000. 10. A composition according to any of the preceding claims, manufactured as a solid, preferably uncoated dosage units.