MX2007010950A - Use of detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines. - Google Patents

Abstract

The invention relates to using detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines, in particular, in diesel engines provided a common rail injection system. The invention relates to using detergent additives for reducing a particle amount in the exhaust gas of direct injection diesel engines, in particular, in diesel engines provided a common rail injection system. The invention relates to novel oxindol derivative of general formula (I), wherein substituents R¹, R², A, B and Y are such as defined in a claim 1. Drugs containing said derivatives and the use thereof for preventing and/or treating vassopress-and/or oxytocin-dependent-diseases are also disclosed.

Description

USE OF DETERGENT ADDITIVES TO REDUCE THE AMOUNT OF PARTICLES IN THE EMISSIONS OF MOTOR EXHAUST GASES DIRECT INJECTION DIESEL Description The present invention relates to the use of detergent additives for the reduction of the amount of particles in the exhaust gas emissions of direct injection diesel engines and especially of diesel engines with common rail injection systems (" common rail "). In direct injection diesel engines the fuel is injected through a multi-orifice injection nozzle of the engine that goes directly into the combustion chamber and disperses very finely (atomization), instead of being introduced into a turbulence chamber or antechamber as in the classic (camera) diesel engine. The advantage of direct injection diesel engines lies in their higher power for diesel engines and yet with lower consumption. In addition, these engines already reach a very high torque at low revolutions. Currently, three processes are mainly used to inject the fuel directly into the combustion chamber: the conventional distributor pump, the pump-nozzle system ("Unit-In ector- System "or" Unit-Pump-System ") and the common conduit system.

In the common duct system, diesel fuel is transported by a pump with pressures up to 2000 bar in a high pressure pipe, the common conduit (literally "common pipe"). From the common duct, bypass pipes are drawn to the different injectors, which inject the fuel directly into the combustion chamber. Thus, in the common duct, all the pressure will always be present, which allows a multiple injection or a special injection form. In the other injection systems, on the other hand, only one injection is possible. The injection into the common duct is basically divided into three groups: (1.) the pre-injection, by which basically a smoother combustion is achieved, so that the hard combustion noises ("pistoneo") and the Engine running is smooth; (2.) the main injection, which is especially responsible for the good development of the torque; and (3.) post-injection, which is responsible for a low NOx value. In this post-injection the fuel is generally not burned, but it is evaporated in the cylinder by residual heat. The exhaust gas / fuel mixture thus formed is transported to the exhaust gas installation where the fuel acts as a reducing agent for NOx nitrogen oxides in the presence of suitable catalysts.

By the variable injection, individual per cylinder, the discharge of harmful substances from the engine can be positively influenced in the common duct injection system, e. , the discharge of nitrogen oxides (N0X), carbon monoxide and especially particles (soot). This allows, for example, that engines equipped with common rail injection systems can theoretically comply with the Euronorm 4 also without additional particulate filter. The specifications on exhaust gases of Euronorm 4 (EU 4) that should lead to a higher purity of air in Europe, require the maintenance of certain limit values, which must be met not only in the factory set-up, but also after a motor running time of 100,000 km and measured under certain test conditions. Thus, the limit value for the ejection of diesel engine particles is 0.025 g / km. Tests of the applicant determined that during the operation of the engine in direct injection diesel engines and especially in those with a common duct injection system, there is an increase in the ejection of particles. This is due, among others, to the formation of deposits in the injection system. For example, coke deposits can be formed in the injection nozzle; but deposits can also be formed in other parts of the injection system. Especially deposits can be formed in the injectors, which causes them to have a different reaction behavior, so that the fuel is no longer injected more in the correct dosage, that is, the injected amount is diverted upwards or downwards with regarding the initial adjustment. The deposits can also cause the fuel to no longer be atomized with the droplet size sufficiently small and / or with the correct geometry. In general, the formation of deposits means that with the increase in the number of kilometers, combustion becomes increasingly sub-optimal, especially increasingly incomplete and thus occurs under coking / soot formation, which leads to that the quantity of particles in the gas emissions of the motor increases and therefore that the limit values of the Euronorm 4 can not be fulfilled for long periods of time or only with the help of complicated and expensive particle filters. The object of the present invention was therefore to provide additives that reduce the ejection of particles that increases with the time of operation of the engine, reducing or avoiding e.g. , among others, the formation of deposits in the injection system of direct injection diesel engines, especially in fuel injection systems. common conduit. The object is achieved by the use of an additive composition composed of at least one detergent additive and optionally at least one vehicle oil for the reduction of the amount of particles in the exhaust gas emissions of direct injection diesel engines. Direct injection diesel engines are especially those with common rail injection systems. In these it is considered that the reduction in the expulsion of particles is due to the reduction or avoidance of the formation of deposits especially in the injectors. In the context of the present invention, the term "particle" has the same meaning as in Euronorm 4. Detergent additives The detergent additives are preferably amphiphilic substances, which have at least one hydrophobic hydrocarbon radical with a molecular weight. number average (Mn) from 85 to 20,000 and at least one polar group, selected from: (a) mono- or polyamino groups with up to 6 nitrogen atoms, wherein at least one nitrogen atom possesses basic properties; (b) nitro groups, optionally in combination with hydroxyl groups; (c) hydroxyl groups in combination with mono- or pol-amino groups, wherein at least one nitrogen atom possesses basic properties; (d) carboxyl groups or other salts of alkali metals or alkaline earth metals; (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts; (f) pol? ox? -C2-C4-alkylene groups which are terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom possesses basic properties, or by carbamate groups; (g) ester groups of carboxylic acids; (h) groups derived from the anhydride of succinic acid with hydroxy and / or amino and / or amido and / or lido groups; and / or (i) groups produced by Mannich reaction of phenols substituted with aldehydes and mono- or polyamines. The rest of hydrophobic hydrocarbon in the aforementioned detergent additives, which ensures that there is sufficient solubility in the fuel, has a number average molecular weight (Mn) of 85 to 20,000, especially of 113 to 10,000, mainly of 300 to 5,000 . As a typical hydrophobic hydrocarbon radical, especially in relation to the polar groups (a), (c), (h) and (i), long-chain alkyl or alkenyl groups are suitable, especially of the polypropenyl, polybutenyl and polusobutenyl moiety with, in each case, Mn = 300 to 5,000, especially 500 to 2,500, mainly 700 to 2,300. As examples of the aforementioned groups of detergent additives, the following are mentioned: Additives containing mono- or polyamino groups (a) are preferably polyalkenomono- or polyalkenepolyamma based on polypropylene or conventional polybutene or polybutene (i.e., mainly with intermediate double bonds), with Mn = 300 to 5,000. If the polybutene or polusobutene base is mainly used in the manufacture of additives with intermediate double bonds (mostly in the beta and gamma position), the preparation can be carried out by chlorination and subsequent animation or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent ammation to reducing (moisturizing) conditions. For the animation can be used here amines, as for example. , ammonia, monoamines or pollamines, such as dimethylaminopropilamma, ethylenediamma, diethylenetriamine, triethylenetramma or tetraethylenepentam. The corresponding additives based on polypropylene are described in particular in O-A-94/24231. Other preferred additives containing monoamino groups (a) are the hydration products of the products of polusobutene reaction with a mean degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946. Other preferred additives containing monoamino groups (a) are the compounds obtainable from polusobutene epoxides by reaction with amines and dehydration and subsequent reduction of the ammoalcohols, as described in DE-A-196 20 262 in particular. additives containing nitro groups (b), optionally in combination with hydroxyl groups, are preferably reaction products of polyusobutenes of average polymerization degree P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-96/03367 and WO-A-6/03479. These reaction products generally represent mixtures of pure nitropolusobutenes (e.g., a, β-dmitropolusobutene) and mixed hydroxynitropolusobutenes (e.g., a-nitro-β-hydroxypolusobutene). The additives containing hydroxyl groups or in combination with mono- or polyamino groups (c) are especially reaction products of polusobutene epoxides, which can be obtained from polusobutene which it preferably has, in particular, terminal double bonds with Mn = 300 to 5,000, with ammonia, mono- or polyamines, as described in particular in EP-A-476 485. The additives containing carboxyl groups or their alkali metal salts or The alkaline earth metals (d) are preferably copolymers of C2-C40 olefins with maleic acid anhydride having a total molar mass of 500 to 20,000, the carboxyl groups of which are reacted in whole or in part to the alkali metal or alkaline earth metal salts and a The remaining residue of the carboxyl groups was reacted with alcohols or amines. These additives are known in particular from EP-A-307,815. Such additives serve mainly to prevent wear of the valve seats and may be used, as described in WO-A-87/01126, advantageously in combination with common fuel detergents such as poly (iso) buteneamines or polyetherammas. The additives containing sulphonic acid groups or their alkali metal or alkaline earth metal salts (e) are preferably alkali metal or alkaline earth metal salts of an alkyl ester of sulfosuccinic acid, as is especially described in EP-A-639,632. Such additives serve mainly to prevent wear of the seats of valves and may be used, advantageously in combination with common fuel detergents such as poly (iso) butenammas or polyetherammas. The additives containing pol? Ox? -C2-C4-alkylene groups (f) are preferably polyether or polyetheramines, which can be obtained by reacting C2-C6 alkanools / C6-C30 alkanediols, mono-di? C2-C3o alkylamines, C3-C30 alkylcyclohexanols or C1-C30 alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or group arrimo and, in the case of poliéteram as, by a subsequent reduction animation with ammonia, monoam or polyammas. Such products are described especially in EP-A-310,875, EP-A-356,725, EP-A-700,985 and US-A-4,877,416. In the case of polyethers, such products also comply with the properties of the vehicle oil. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylate, as well as butoxylates and polyusobutenol propoxylates, as well as the corresponding reaction products. The additives containing ester groups of carboxylic acids (g) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those with a minimum viscosity of 2 mm2 / s at 100 ° C, as describe especially in the DE-A-38 38 918. Aromatic or aliphatic acids may be used as mono-, di- or tricarboxylic acidsalcohols and / or ester polyols are suitable, in particular, long chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, iso-phthalates, terephthalates and octanol, iso-nonanol, iso-decanol and isotridecanol. Such products also have vehicle oil properties. The additives containing groups derived from succinic anhydride with hydroxy and / or ammo and / or amido and / or amido groups (h) are preferably the corresponding derivatives of the succinic anhydride substituted with alkyl or alkenyl and especially the corresponding derivatives of the anhydride of polusobutenylsuccinic acid, which can be obtained by the reaction of conventional polyusobutene or highly reactive with Mn = 300 to 5000 with maleic anhydride either thermally or through chlorinated polybutene. Of special interest are the derivatives with aliphatic polyamines, such as ethylenediamine, diethylene glycine, tetylenetetramma or tetraethylenepentam. In the groups with hydroxy groups, and / or ammo and / or amido and / or amido, it is, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines, which in addition to the function amide they still have free amine groups, succinic acid derivatives with a function of acid and amide, carboxylic acid amides with monoamines, carboxylic acid esides with di- or polyamines, which in addition to the amide function still have free amine groups, or dumides that are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are described especially in US-A-4,849,572. The additives containing groups produced by the Mannich reaction of phenols substituted with aldehydes and mono- or polyamines (i) are preferably reaction products of phenols substituted with polusobutene, with formaldehyde and mono- or polyamines, such as ethylene diamine, diethylene triamma, tetramethyl, tetraethylenepentam or dimethylamine propylamine. Phenols substituted with polusobutenyl can come from conventional polyusobutene or highly reactive with Mn = 300 to 5000. Such "Mannich bases of polusobutene" are described especially in EP-A-831,141. For a more precise definition of the fuel additives mentioned individually, reference is expressly made herein to the descriptions in the above-mentioned articles of the prior art. Especially preferred are the detergent additives of the group (h). Preferably, the reaction products of alkyl or alkenyl-substituted succinic anhydrides, especially of polyisobutenyl-succinic acid anhydrides, are treated with amines. It is understood that these reaction products can be obtained not only by the use of the substituted succinic acid anhydride, but also by the use of substituted succinic acid or suitable acid derivatives, such as halides or esters of succinic acid. Especially preferred detergent additives are imides of succinic acid subsituted with polyisobutenyl, especially the imides with aliphatic polyamines. Particularly preferred polyamines are diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, with tetraethylenepentamine being particularly preferred. The polyisobutenyl radical has a number-average molecular weight M n, preferably from 500 to 5000, in particular from 500 to 2000 and most especially from approx. 1000. It is understood that the detergent additives may be used alone or in combination with at least one of the aforementioned detergent additives. In a preferred embodiment, the detergent additive is used in combination with at least one carrier oil.

Vehicle oils Suitable mineral vehicle oils are fractions resulting from the production of petroleum such as Bpghtstock or base oils with viscosities, such as, for example, class SN 500-2000, but also aromatic hydrocarbons, paraffined hydrocarbons and alkoxyalkanols. A fraction known as hydrocracking oil resulting from the refining of mineral oil (vacuum distillation with a boiling range between 360 and 500 ° C, which can be obtained from dewatered natural mineral oil as well as catalytically hydrolyzed and isomerized under high pressure). Mixtures of the carrier oils mentioned above are also suitable. Examples of synthetic vehicle oils usable in accordance with the invention are selected from: polyolefms (polyalphaolefms or internal polyolefms), (poly) esters, (poly) -alkoxylates, polyethers, aliphatic polyetheramines, polyethers initiated with alkylphenols, polyetheramines initiated with alkylphenol and esters of carboxylic acids of long chain alkanols. Examples of suitable polyolefms are olefin polymers with Mn = 400 to 1800, especially based on polybutene or polusobutene (hydrated or unhydrated). Examples of suitable polyethers or polyetherramms are preferably compounds containing polyoxy-C-C4 alkylene groups, which can be obtained by reaction of C2-C60 alkanols, C6-C30-alkanediols, C2-C30 mono- or dialkylamines, alkylcyclohexanols-Ci-Cso or C-C30 alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by a subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described especially in EP-A-310,875, EP-A-356,725, EP-A-700,985 and US-A-4,877,416. For example, poly-alkyleoxydiamines-C2-C6 or functional derivatives thereof can be used as polyetherramines. Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylate, as well as butoxylates and polyisobutene propoxylates, as well as the corresponding ammonia reaction products. Examples of esters of carboxylic acids of long-chain alkanols are especially esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in DE-A-38 38 918. As mono-, Di-or tricarboxylic acids can be used aromatic or aliphatic acids, as esters of alcohols and / or polyols are especially suitable long chain representatives with, for example, 6 to 24 C atoms. Representatives Typical of the esters are the adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, as eg. , di- (n- or iso-tridecyl) phthalate. Other suitable vehicle oil systems are described, for example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0 452 328 and EP-A-0 548. 617, to which reference is expressly made hereby. Examples of particularly suitable synthetic vehicle oils are polyethers initiated with alcohol with approx. 5 to 35, as per e. , 5 to 30 units of C3-C6 alkylene oxide, as per e. , selected from units of propylene oxide, n-butylene oxide and i-butylene oxide, or mixtures thereof. Non-limiting examples of suitable starting alcohols are long-chain alkanols or phenols substituted with long-chain alkyls, wherein the long-chain alkyl moiety represents especially a linear or branched C6-C?-Alkyl radical. Preferred examples are tridecanol and nonylphenol. Other suitable synthetic vehicle oils are the alkoxylated alkylphenols, as described in DE-A-10 102 913.6. Preferred vehicle oils are synthetic vehicle oils, wherein polyether is especially preferred.

The detergent additive, optionally in combination with a carrier oil, is supplied to the injection system preferably with diesel fuel. Thus, the detergent additive or the mixture of different detergent additives is added to the diesel fuel in an amount of preferably 10 to 2000 ppm by weight, especially 20 to 1000 ppm by weight, more preferably 50 to 500 ppm by weight and more preferably still from 50 to 200 ppm by weight, e.g. , from 70 to 150 ppm by weight. When a carrier oil is used, it is added to the diesel fuel in an amount of preferably 1 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight and more preferably still from 20 to 100 ppm by weight. In addition, diesel fuel may contain other common co-additives, such as cold flow improvers, corrosion inhibitors, demulsifiers, antifog agents, defoamers, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents. , metallocenes, metal deactivators, dyes, solvents, and the like. It is assumed that the use of these additives in general has no influence on the reduction of particle ejection. Suitable cold flow improvers are eg. , copolymers of ethylene with at least one other ethylenically unsaturated monomer, e.g. , ethylene / vmilo acetate copolymers. Suitable corrosion inhibitors are e.g. , succinic acid ester, especially with polyols, fatty acid derivatives, eg. oleic acid ester, oligomerized fatty acids, substituted ethanolamm and products that are marketed under the trade name RC 4801 (Rhem Chemie Mannhem, Germany) or HiTEC 536 (Ethyl Corporation). Suitable de-emulsifiers are e. , the alkali or alkaline earth salts of naphthalene and phenol sulfonates substituted with alkyl and the alkali or alkaline earth salts of fatty acids, furthermore neutral compounds, such as alcohol alkoxides, as per e. , alcoholetoxylate, phenol alkoxylate, e. , tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), by e. , also in the form of EO / PO block copolymers, polyethyleneimine or also polysiloxanes. Suitable antirust agents are e.g. , alkoxylated formaldehyde-phenol condensates, for example, the products obtainable under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

Suitable defoaming agents are e.g. , polysiloxanes modified with polyether, as for example, the products that can be obtained under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc). Improvers of the number of suitable cetans are eg. , aliphatic nitrates, such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides, such as di-tert-butyl peroxide. Suitable antioxidants are eg. , substituted phenols, such as 2,6-di-tert-butylphenol and, 6-di-tert-butyl-3-methylphenol, and phenylenediamines, such as N, N'-di-sec-butyl-p-phenylenediamine. Suitable metal deactivators are e.g. , salicylic acid derivatives, such as N, N '-disaliciliden-1, 2-propandia ina. Suitable solvents are e.g. , non-polar organic solvents, such as aromatic and aliphatic hydrocarbons, for example, toluene, xyloles, "white spirit" and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and organic solvents polar, for example, alcohols, such as 2-ethylhexanol, decanol and isotridecanol. Preferred co-additives are demulsifiers, antifog agents, antifoaming agents, number improvers of cetans, antioxidants, metal deactivators, corrosion inhibitors and solvents. These common co-additives, when required, are added for it in usual amounts. Diesel fuels Diesel fuels are, for example, petroleum refined products that commonly have a boiling range of 100 to 400 ° C. These are mostly distilled with a point of 95% up to 360 ° C or more as well. These can also be the so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a point of 95% of, for example, a maximum of 345CC and a sulfur content of, for example, a maximum of 0.005% by weight or by a point of 95%, for example, 285 ° C and a sulfur content of at most 0.001% by weight. Along with the diesel fuels that can be obtained by refining are those obtained by coal gasification or coal liquefaction ("gas to liquid" fuels (GTL)). Mixtures of the aforementioned fuels with regenerative fuels, such as biodiesel or bioethanol, are also suitable. Among diesel fuels, those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.22% by weight, especially less than 0.005% by weight, are especially preferred. and very especially less than 0.001% by weight. By the use of the detergent additives according to the invention it is achieved that the exhaust gas emissions of direct injection diesel engines, especially of diesel engines with a common duct injection system, the increase of the amount of particles is much less than in the emissions of exhaust gases of direct injection diesel engines that work without the use of detergent additives. It is especially achieved that after 100,000 km of operation of a motor, the quantity is preferably at most 2.5 times, especially at most 2.2 times the quantity, and very especially at most 2 times the number of particles, compared with the set-up at the factory. The quantities of particles contained in the exhaust are particularly clearly below the limit value of Euronorm 4. The values given relate to the exhaust gas emissions taken directly behind the engine ("engine out"), ie before a particle filter mounted eventually, which would reduce the amount of particles in the exhaust. Factory set-up means the status of the direct injection diesel engine or the injection system, as set in the factory, ie before delivery to the dealer or to the end user (the so-called 0 kilometer) Due to the use of detergent additives according to the invention, not only compliance with the limit values for the emission of particles according to Euronorm 4 is guaranteed, even without an additional particulate filter during a motor running time of 100,000 km, but also for an operating time well beyond this value. Example A 70,000 km engine was run with a common rail injection system, with a diesel fuel according to EN 590 containing 90 ppm by weight of a Kerocom PIBSI additive (a BASF AG detergent additive, which contained an acid imide). polyisobutylene-succinic). To compare, an engine of the same construction was started with a diesel fuel according to EN 590 that did not contain detergent additive under the same conditions also 70,000 km. The quantities of particles contained in the exhaust were measured directly behind the engine ("engine out"). The results are shown in the following table.

Table As the results show, the use of detergent additives leads to a smaller amount of particles in the exhaust gases.

Claims (6)

1. CLAIMS 1. Use of an additive composition composed of at least one detergent additive and optionally at least one vehicle oil for the reduction of the amount of particles in the exhaust gas emissions of direct injection diesel engines.
2. 2. Use according to claim 1, for reducing the amount of particles in the exhaust gas emissions of diesel engines with common rail injection systems.
3. Use according to one of the preceding claims, characterized in that the detergent additives are reaction products of succinic acids substituted with alkyl or alkenyl or derivatives thereof with amines.
4. 4. Use according to claim 3, characterized in that the detergent additives are succinic acid imides substituted with polyisobutenyl.
5. Use according to one of the preceding claims, characterized in that the detergent additives are used in combination with at least one carrier oil.
6. 6. Use according to one of the preceding claims, characterized in that the amount of particles contained in the exhaust emissions of the engines Diesel and measurements directly behind the engine after a motor operation of 100,000 km is greater by a factor of at most 2.5 times than that of the factory set-up and simultaneously does not exceed the limit value for the amount of particles of Euronorma 4.