JPH04506681A - fuel additive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] fuel additive composition Background of the invention Hydrocarbon fuels inherently contain a large number of deposit-forming substances. These substances are , when used in an internal combustion engine, the narrow area of the internal combustion engine that the fuel comes into contact with and tend to form deposits around them. Commonly and sometimes markedly in the formation of deposits Typical areas that are overloaded are carburetor air bleeds and slots. body and venturi, engine intake valve and intake port, fuel injection nozzle, cylinder - There are surfaces of the combustion chamber of the head and piston top.

Deposits adversely affect the operation of vehicles using hydrocarbon fuels. For example, cab Deposits on the letter throttle body and venturi prevent the gas mixture from entering the combustion chamber. Increases the fuel-to-air ratio and therefore unburned hydrocarbons and monoacids that are emitted from the combustion chamber The amount of carbonized carbon increases. A high fuel-to-air ratio also increases the mileage per gas that a vehicle can achieve. Reduce line distance.

Sufficiently heavy deposits on the engine's intake valves prevent the gas mixture from entering the combustion chamber. Restrict. This restriction starves the engine of air and fuel, reducing power output. . Deposits on intake valves can also cause valve damage due to combustion and improper valve seating. Increase your chances. In addition, these deposits can flake off and enter the combustion chamber, possibly on the piston. cause mechanical damage to the engine top, piston rings, cylinder head, etc.

The formation of these deposits can be removed by incorporating active detergents into the fuel. It has been known for a long time that it is not only possible, but can even be suppressed. child These cleaning products work by cleaning these areas where harmful deposits are likely to build up. This increases engine performance and lifespan.

The first generation of fuel additives helps maintain the cleanliness of critical carburetor elements. It consisted of a cleaning agent. These early fuel additives were used in small doses, typically Doses in the range of 15-30 ppm were typically used. unfortunately , these small doses of additives provide little control over deposition in other parts of the combustion engine. Almost nothing was done.

The next generation of fuel additives will generally address intake manifold hot spots, runners, Improved deposition control in the intake system, including the air valve opening and intake valve. Deposition The degree of control is typically determined by varying the dosage of the additive, usually from 70 to 2,000 It was regulated by controlling in the ppm range. However, the dosage of additives is high As the level increases, the accumulation of deposits in the combustion chamber or This has become a serious issue for several reasons.

Unleaded gasoline has become widely used in recent years, but this does not mean that cleaning agent-type gasoline Further complicating the use of solin additives. Use of unleaded gasoline (lowers emissions) (to prevent disabling of catalytic converters used in engine, sufficient to prevent knocking and associated damage. Providing gasoline with sufficient octane ratings proved difficult. . This problem is due to increased octane requirements (octa), referred to herein as "ORI". The increase in The addition is the result of deposits formed by the use of commercial gasoline.

The basics of the ORI problem are as follows: each engine is After driving, the engine should operate satisfactorily without pinging and/or knocking. requires fuel with a certain minimum octane rating to operate. Is it an engine? As gasoline is operated, this minimum octane requirement increases. this child This is apparently caused by the formation of deposits in the combustion chamber. Haton In which cases will an engine run on the same fuel for a long period of time flatten its ORI? Reach equilibrium. Typically after driving the car for 5,000 to 15,000 miles equilibrium is reached.

The increase in octane requirements for certain engines using commercial gasoline is 4 to 6 depending on gasoline composition, engine design and type of operation. It varies from octane units to as high as 12 to 15 octane units. of this problem The significance is thus clear. A typical car with a research octane requirement of 85 Or when it is a new car, research octave is required for proper driving after several months of driving. Most require gasoline with an octane rating of 97, or most unleaded gasoline with that octane rating. I can't get it.

The OR,1 problem also exists to some extent with engines operated on leaded fuel. . U.S. Patent Nos. 3,144,311, 3.146.203 and 4.2 No. 47.301 discloses the properties of ORr and reduced lead-containing fuel compositions. It will be done.

The ORr issue is the most common way to increase the octane rating of unleaded gasoline. Complicated by the fact that increasing the aromatic content of these Aromatics, however, end up causing an even greater increase in octane requirements. wake up In addition, nitrogen content, which is currently used as a deposition control additive, compounds and their mineral oil or polymeric carriers may also use unleaded fuel. This may be a major cause of ORI problems in engines.

Therefore, deposits in the engine intake system do not significantly contribute to ORI problems. Deposition control additives that work at dosages sufficient to effectively control It is particularly desirable to provide In this regard, the dispersant hydrocarbyl poly(oxyalkylene) aminocarba Control mate or induction system deposits without significantly contributing to ORI problems. It is a commercially successful fuel additive. However, these additives are relatively expensive. , which precludes their use in high concentrations.

In economical fuel concentrations, hydrocarbyl poly(oxyalkylene) aminocarbamates Cleans deposits in the injectors or carburetors of modern combustion engines. cannot be said to be extremely effective in controlling This includes the fuel injection fuel delivery system. engine performance can be substantially impaired by relatively small amounts of deposits. There is a nature.

On the other hand, low molecular weight hydrocarbylamine and polyamine cleaning agents or injectable It is known to effectively control deposits in vectors. these Amine-based cleaners similar to those used above to keep the carburetor clean belongs to. However, in order to control deposits on the injector, These detergents are used at fuel concentrations ranging from 40 to 70 ppm.

Such high doses of injector cleaners are harmful to the engine's intake valves and Currently known to have a negative impact on the control of deposits in the combustion chamber. Ru.

Certain low molecular weight hydrocarbyl amine systems with primary and secondary amine functionality Application problems with polyamine and polyamine detergents arise when the amine is exposed to carbon dioxide. , for example by forming a solid precipitate when exposed to carbon dioxide in the air. Ru. This precipitate is formed by the reaction of primary or secondary amines with carbon dioxide. It is thought to be a rubamic acid adduct. Regardless of its chemical structure, something like this Precipitate formation is undesirable for reasons explained below.

Certain low molecular weight amines, especially those with polar substituents, e.g. Yet another problem associated is that these amines have a high degree of water solubility and therefore do not come into contact with water. There is a possibility that the amine can be completely extracted from the hydrocarbon phase into the aqueous phase. That is. As a result, the effectiveness of such amines in hydrocarbon fuels is reduced. It will be.

In this regard, U.S. Pat. No. 4,810,263 describes contamination in multi-mouth engines in which fuel is injected. An additive package for reducing and/or preventing is disclosed. This additive pack The cage is an amine oxide, e.g. bis(2-hydroxyethyl) cocamine oxy and reaction products of fatty acid alkyl amines, and oxyalkylated alkyl One type selected from solutions of phenol formaldehyde resin and polyglycol Or it contains a demulsifier consisting of two or more types of demulsifiers. Granted to Zimmerman et al. U.S. Pat. No. 4,836,829 discloses that the combined tertiary amines, such as bis(2-hydroxyethyl)cocamine, and A similar additive package containing a demulsifier is disclosed. This amine oxide is typical, as recognized in U.S. Pat. No. 4,810,263. contains water that is difficult to completely remove due to its manufacturing process. including.

As a result, the amine oxide was dissolved in isopropyl alcohol containing 6-8% by weight of water. It is commercially available as a liquid.

Mineral oil-based carriers or often amine-based carriers are used to help remove or prevent deposits. Detergent or hydrocarbyl poly(oxyalkylene) aminocarbamate dispersant Used with either. However, even with the addition of mineral oil-based carriers, Neither group of fuel additives provides complete intake system deposition control.

Therefore, intake valve and combustion chamber deposition control additives, such as hydrocarbyl Cleaning poly(oxyalkylene)aminocarbamate dispersant for injectors agent, such as a low molecular weight amine or polyamine, and an effective amount of a carrier fluid. for effective control of deposits throughout the engine intake system and combustion chamber. , and does not itself make a significant contribution to the problem of increasing octane requirements. It would be particularly desirable to provide a multi-component, multi-functional fuel additive package. .

Selection of ingredients for multi-component, multi-functional deposition control fuel additive compositions is easy. There is no single one. This composition has an economical additive level and additives that do not contribute to ORr. Additives must provide effective deposition control.

The composition also changes when it is blended with fuel and when the engine actually operates. If the expected performance of deposition control should be reliably demonstrated when It is essential that it remains homogeneous under all field conditions, i.e. a single liquid phase. be.

It is important to maintain a single liquid phase when providing an effective fuel additive composition . Typically, once the additive composition has been distributed in the fuel field, it is rehomogenized. There is no practical way to do so. Large amounts of additive compositions may result from incompatibility of the components. In the case of separation into more than one phase, none of the phases can effectively combine the components intended for the fuel. Does not include matching. Therefore, the overall deposition control performance of this fuel is seriously It deteriorates as much as possible. Moreover, the additive composition delivered to the fuel is variable.

Phase separation of incompatible compositions can take many forms. Typically, phase separation begins with a cloudy It appears as This haze may ultimately be either higher or lower depending on the relative densities of the two phases. Precipitates or precipitates in either of the following. Thus, for example, the level of additives in the storage tank As the liquid is drawn down, the interface between the phases becomes the liquid draw point. aint), at which point the additive composition entering the fuel is It will probably change drastically.

Phase separation also poses significant problems in additive distribution systems that distribute additive compositions into fuels. wake up If phase separation involves two liquid phases, the heavier phase is stored in the additive storage tank. Collects at the bottom and at low points in the additive delivery line. As a result, the cost of additive distribution equipment is reduced. This requires inconvenient periodic cleaning.

The effects are even more pronounced when phase separation or solids separate from bulk liquid additive compositions. Significant and immediate.

Fact 1: All additive injection systems are finely tuned to protect the injection pump valves and seals. Equipped with mesh filter. The solid phase quickly blocks these filters. , causing the injector to stop working, thus restarting the injector It will be necessary to clean the filter beforehand. A separate solid phase can also be used to store additives. Regular cleaning of storage tanks will also be required. Thus, a homogeneous additive composition The criticality is clear.

Including small amounts of fuel/hydroemulsifying substances in the fuel blend of the additive composition is generally considered to be advantageous. Demulsifiers are relatively low in motor fuels. demulsifying properties when used at levels such as 5 to 25 parts per million. must be shown. However, even at low dosages, such substances exhibit certain characteristics. In certain instances, it can have a negative impact on the deposition control properties of additive compositions. It has been observed. Therefore, choose a demulsifier that does not exhibit this negative effect. It is desirable to do so.

In addition, it is important that the demulsifier remains homogeneous with the additive composition for the reasons mentioned above. It is essential.

It is also generally advantageous to include a solvent or diluent in the additive composition. this The primary function of the component is to reduce the low temperature viscosity of the composition. Solvents, however, It must be compatible with the excipient ingredients and be economical.

Related technology U.S. Pat. No. 4.160.648 and U.S. Pat. No. 4.191.537 disclose Hydrocarbyl poly(oxyalkylene) aminocarbame as an additive]・ will be disclosed.

A fuel-soluble carrier oil and also a demulsifier can be Also disclosed are combinations with kylene) aminocarbamates.

Using hydrocalhylamines and hydrocalhylic polyamines as fuel additives is disclosed in the following US patent specifications: U.S. Pat. No. 3,438,757; No. 3.565.804, No. 3.574.576, No. 3.898.056 No. 3.960.515.

U.S. Pat. No. 3,898,056 and U.S. Pat. No. 3,960,515 disclose fuel High and low molecular weight hydrocarbons used as detergents and dispersants at low concentrations in A mixture of carbylamines is disclosed. High molecular weight hydrocalhylamines have molecular weight or about 1.900 to 5.000 at least one hydrocalyl poly On the other hand, low molecular weight hydrocalhylamines have a molecular weight of about 300 to 600. It has at least one hydrocarbyl group. Low molecular weight amines in mixtures The weight ratio of high molecular weight amine to high molecular weight amine is maintained at about 0.5:1 to 5.1.

These documents describe hydrocarbyl poly(oxoalkylene) amines useful as dispersants. Hydrocarbylamines and polyamines that act as minocarbamates and detergents or contribute to the OR1 problem when mixed with fuel at low concentrations in these documents. provides effective deposition control throughout the entire intake system while minimizing A homogeneous additive composition comprising a powder, a detergent, a carrier oil and a demulsifier is taught. There is nothing to show.

Summary of the invention The present invention comprises the following components: (a) having at least one basic nitrogen atom, with an average molecular weight of about 1.　o　o o~about 3. OOO hydrocarbyl poly(oxyalkylene) aminocarba A dispersant comprising mate.

(b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to about 7; 00 branched chain hydrocarbylamine, the hydrocarbyl moiety of which is C2~ Contains hydrocarbyl amines that are derived from polymers of C8 olefins. Injector cleaning agent consisting of: (C) What are the other components of the final fuel additive composition? a fuel demulsifier that is homogeneous; and (d) carrier fluid, natural or synthetic; A novel, homogeneous fuel additive composition comprising:

The invention further relates to hydrocarbons boiling in the range of gasoline or diesel and parts per million. a fuel comprising about 400 to 1.200 parts of the homogeneous fuel additive composition of "C" A composition is provided.

The present invention also provides boiling water in the range of 150-400'F (65.6-204.4°C). an inert, stable, lipophilic organic solvent and about 5 to 50% by weight of the homogeneous fuel of the present invention. The present invention relates to a fuel concentrate comprising a fuel additive composition.

Among other factors, the present invention utilizes the dispersants described herein, low molecular weight injectable A unique combination of detergent, demulsifier and carrier fluid correlates with ORI Complete deposition of the intake system with minimal associated attenuating deposits in the combustion chamber Based on the surprising discovery that it gives you control.

In addition, it is used as a cleaning agent for low molecular weight branched chain hydrocarbylamine injectors. The use of detergents with known amine-based detergents, e.g. This avoids the problem.

Detailed description of the invention In summary, the present invention adds to conventional fuel additives, whether alone or concentrated. Complete deposition control of gasoline intake systems, whether typical use of combinations Addresses the problem associated with the fact that there is no single rule that can be given. It is something to do. The present invention provides maximum deposition control in each critical region of deposit formation; Demonstrates a new formulation technique that simultaneously minimizes the dosage of each critical ingredient It is. As a result, the overall deposition control performance of the intake system and combustion chamber It is now possible to minimize the negative effects of individual components.

The present invention provides a compatibility solution for deposition control additives and carrier fluids and oils. Describes a fuel additive composition that provides a homogeneous mixture with an emulsifier . Deposition control additives and carrier fluids are defined by their respective effectiveness. Historically recognized for maintaining adequate inspiratory system deposition control in the individual rates are significantly lower than the levels previously reported.

Accordingly, the novel fuel additive composition of the present invention has the following components: (a) having at least one basic nitrogen atom, with an average molecular weight of about i,o　o o~about 3. OOO hydrocarbyl poly(oxyalkylene) aminocarba Dispersant comprising mate: (b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to about 7; 00 branched chain hydrocarbylamine, the hydrocarbyl moiety of which is C2- C, containing hydrocarbylamines derived from polymers of olefins. (C) an injector cleaner comprising: (C) an injector cleaner comprising: quality fuel demulsifier: and (cl) A homogeneous mixture comprising a natural or synthetic carrier fluid.

Generally, the homogeneous fuel additive compositions of the present invention contain about 10 to 70% by weight of the above amino acids. Rubamate dispersant, about 1 to 0% by weight of the above hydrocarbylamine injector. about 0.5-5% by weight of the above fuel demulsifier and about 25-80% by weight % of the above carrier fluid.

Although the fuel additive compositions of the present invention can be used neat, The composition is often diluted with an inert solvent or diluent to a dilution of about 50% or less. is desirable.

dispersant The dispersant used in the homogeneous fuel additive composition of the present invention has at least one basic It has a nitrogen atom and has an average molecular weight of about 1. Hydrocarbyl from OOO to 3.000 It is a poly(oxyalkylene)aminocarbamate. However, the amount used The powder contains a poly(oxyalkylene) component, an amine component and a carbamate connecting group. In other words, the hydrocarbyl used in producing the carbamate of the present invention Poly-terminated poly(oxyalkylene) polymers are monohydroxy polyethers. or polyalkylene glycol monocarbyl ethers, i.e. “capped” ports. monohydroxy compounds, often referred to as ly(oxyalkylene)glycols, For example, an alcohol that is not terminally hydrocarboxylated, i.e., is a capacitor. poly(oxyalkylene) glycol (diol) or polyol It is a special thing that is distinguished from ru.

Hydrocarbyl-terminated poly(oxyalkylene) alcohols are lower alkylene oxidants such as ogisolan, ethylene oxide, propylene oxide, petit Produced by adding ren oxide etc. to a hydroxy compound under ROH polymerization conditions. will be built. However, in the above formula, R caps the poly(oxyalkylene) chain. It is a hydrocarbyl group. The poly(oxyalkylene) composition used in the present invention In minutes, the group R generally has from 1 to about 30 carbon atoms, preferably from 2 to about 20 carbon atoms. containing carbon atoms, which are aliphatic or aromatic, i.e., having an alkyl group of from 1 to about Alkyl or alkyl groups, straight or branched, having 24 carbon atoms Preferably, it is phenyl.

More preferably, R is a propylene group in which the alkyl group is commonly referred to as tetrapropenyl. A branched alkyl chain with 12 carbon atoms derived from a tetramer of It is henyl. The number of oxyalkylene units in the poly(oxyalkylene) component is 2 to Preferably there are 5 carbon atoms, or 1 unit with a larger number of carbon atoms. Or there may be more. Poly(oxyalkaline) used in the present invention Regarding the xylene component, further details are given in U.S. Pat. No. 4,191,537. , the disclosure of which is incorporated herein by reference. It shall be.

The hydrocarbyl group attached to the hydrocarbyl poly(oxyalkylene) component is Preferably they contain from 1 to about 30 carbon atoms, although longer Drocarbyl groups, especially long chain alkylphenyl groups, may also be used.

For example, U.S. Patent No. 4.881.9 to BubkleY. 45, the alkyl group has at least 40 carbon atoms Alkylphenyl poly(oxyalkylene) aminocarbamates are also included in the present invention. This is the intended use. This U.S. Patent No. 4.881.945 The alkylphenyl group attached to the aminocarbamate has 50 to 20 carbon atoms. Preferably, it contains 0 alkyl groups, and preferably has 60 to 100 carbon atoms. It is more preferable that it contains an alkyl group. This U.S. Patent No. 4,881.945 The disclosure of No.

B. Amine component Hydrocarhyl-terminated poly(oxyalkylene) aminocarbamate amide The carbon moiety is a polyester having 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. Those derived from amines are preferred. Polyamines are used within the scope of the invention. is a hydrocarbyl poly(oxoalkylene) aminocarbamate fuel additive reaction with hydrocarbyl poly(oxyalkylene) chlorormate to produce It is preferable to make it correspond. Chloroformate itself is a hydrocarbyl poly(oxychloride). derived from (sialkylene) alcohols by reaction with phosgene.

Polyamines, including diamines, have a carbamate molecular weight of at least about 1 Poly(ol) of the product grows basic nitrogen atoms, i.e., nitrogen atoms that can be titrated with strong acids. xyalkylene) aminocarbamate. Polyamine is about 1,1 to about 10 It is preferable to have a carbon to nitrogen ratio of =1. Polyamine is hydrogen, L ~ about 10 Hydrocarbyl groups having carbon atoms, acyl groups having from 2 to about 10 carbon atoms , as well as monoketones, monohydrocarbons of hydrocarbyl groups having 1 to 10 carbon atoms. Selected from droxy, mononitro, monocyano, alkyl and alkoxy derivatives may be substituted with selected substituents. Less basic nitrogen atoms in polyamines Preferably, one of each is a primary or secondary amino nitrogen atom. Used in the present invention The polyamine components included are more fully described in U.S. Pat. No. 4,191,537. described and illustrated.

Hydrocarbyl (oxyalkylene) component and amine used in the present invention Hydrocarbyl, used when describing ingredients, is an entity composed of carbon and hydrogen. means a radical, which is aliphatic, cycloaliphatic, aromatic or a combination thereof, e.g. It is possible to be an Aralquil. Hydrocarbyl groups are aliphatic unsaturated, i.e. Relatively free of olenic and acetylenic unsaturation, especially acetylenic unsaturation is preferable. More preferred polyamines of use within the scope of the present invention are alkylene including diamines, and also substituted alkylene polyamines such as alkyl and hydro Polyalkylene polyamines, including xyalkyl-substituted polyalkylene polyamines It is. Preferably, the alkylene group contains 2 to 6 carbon atoms and between the nitrogen atoms Preferably, 2 to 3 carbon atoms are present. An example of such a polyamine is Ethylenediamine, diethylenetriamine, triethylenetetramine, di(triamine) methylene)triamine, dipropylenetriamine, tetraethylenepentamine, etc. There is. Among polyalkylene polyamines, 2 to 12 amine nitrogen atoms and 2 Polyethylene polyamines and polypropylene polyamines containing ~24 carbon atoms Brobylene is particularly preferred, and especially lower polyalkylene polyamines, e.g. Ethylenediamine, diethylenetriamine, propylenediamine, dipropylene Most preferred are triamines and the like.

C1 amino carbamate Poly(oxyalkylene oligoaminocarbamate fuel used in the compositions of the present invention) The additive carbamates the amine and poly(oxoalkylene) components together. i.e. 0-C(0)-N- can be obtained by coupling via . However, oxygen in the formula is poly(oxygen) alkylene) can be considered as the oxygen of the terminal hydroxyl group of the alcohol component, The carbonyl group -C(0)- is also preferably a coupling agent, such as phosge given by In a preferred method of preparation, hydrocarbyl poly(oxo Alkylene) alcohol reacts with phosgene to produce chloroformate This chloroform-1. is reacted with a polyamine. The carbamate bond is , a chloroformate oxo on the poly(oxyalkylene) chain or polyamine nitrogen. It is formed as it is bonded through a carbonyl group.

Polyamines that can react with chloroformates contain one or more nitrogen atoms. Aminocarbamates contain at least one hydrocarbyl. Building poly(oxyalkylene) polymer chains via oxycarbonyl groups The carbamate may contain 1 to 2 or 3 or more carbon atoms. It is possible to grow such polymer chains. Product hydrocarbylpo The average molecular weight of ly(oxyalkylene)aminocarbamates is approximately 1 (oxyalkylene) chain (i.e. is monocarbamate) or The reaction route involves significant amounts of silicon in polyamines containing several reactive nitrogen atoms. - or tri- or more poly(oxyalkylene) chain substitution results in some mixtures. There are some things. Particularly preferred aminocarbamates are amine moieties or ethylenediamine moieties. Alkylphenyl poly( (oxyalkylene) aminocarbamate. Amino acid used in the present invention Synthesis methods, preparation methods and other properties that avoid higher degrees of substitution of nocarbamates are more fully described and illustrated in U.S. Pat. No. 4,191,537. It is.

Injector cleaning agent The injector cleaner used in the homogeneous fuel additive composition of the present invention is Both have one basic nitrogen atom and have an average molecular weight of about 300 to about 700. A branched hydrocarbylamine whose hydrocarbyl moiety is 02-06 It is a branched hydrocarbyl amine derived from a polymer of refine. Ru.

In amine detergents for injectors, the branched hydrocarbyl groups are usually 2- Produced by polymerizing olefins with 6 carbon atoms (branched copolymerized with ethylene or another olefin to give branched chain hydrogen A locarbyl group generally has at least 6 carbon atoms per 6 carbon atoms along its chain. at least 1, more preferably 2 per 1, preferably 4, carbon atoms There is at least one trick per carbon atom. Preferred branched hydrocarbyl The group is polypropylene and polyisobutylene. These techniques usually involve carbon atoms. One or two carbon atoms, preferably one carbon atom, ie, methyl. general In addition, branched hydrocarbyl groups have about 20 to 40 carbon atoms.

In most cases, branched-chain hydrocarbylamines are not pure single products; It is a mixture of compounds having a certain average molecular weight. Molecular weight range is usually relatively narrow , with a peak near the specified molecular weight.

The amino component of branched hydrocalhylamines is either a monoamine or a polyamine. It can be said that it is. The monoamino or polyamino component contains 1 to 10 nitrogen atoms and A wide range of carbon atoms containing 2 to 40 carbon atoms and a carbon-to-nitrogen ratio of about 1:1 to l0 = 1. amines of the group. In most cases, this amine component is a pure single product. rather, it is a mixture of compounds in which the majority is the indicated amine.

For more complex polyamines, their composition contains the specified compound as the main product. It is an amine mixture containing small amounts of related compounds.

If the amine component is a polyamine, it is a polyamine, including alkylene diamines. Lukylene polyamine is preferred. Preferably, the number of alkylene groups is 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.

Examples of such polyamines include ethylenediamine, diethylenetriamine, and triamine. There are tylenetetramine and tetraethylenepentamine.

A particularly preferred branched hydrocarbylamine is polyisobutenylethylenediamine. It is.

Branched-chain hydrocarbyl for injectors used in the fuel additive composition of the present invention Amine detergents are manufactured by conventional methods known in the art. this Such branched hydrocarbyl amines and their preparation are described in U.S. Pat. ．． No. 438.757, No. 3.565.804, No. 3.574.576, It is described in detail in the specifications of the same No. 3.848.056 and the same No. 3.960.515. It is.

The fuel additive composition of the present invention, the disclosure of which is cited and referred to herein. When used at relatively low concentrations in gasoline compositions, demulsifiers used in Static separation of emulsified water with the aid of gravity in a static storage tank Therefore, they coalesce rapidly to the point where they can be effectively removed from large amounts of hydrocarbons. It is a chemical agent that promotes , the second demulsifier is often used in the right combination. It is a mixture of several chemical agents that produce the desired demulsifying properties. these drugs The agent is typically, but not limited to, an alkylphenol resin, a polymer, etc. Lyoquin alkylene based fluids, alkylaryl sulfonates, fatty acid inducers Selected from conductors, etc. One preferred demulsifier for use in the compositions of the invention is located in Missouri and St. Louis. Petrolite Corporation, Toledry De-milking commercially available from Tretolite Division The chemical agent known as Tolad (registered trademark) T-326 , which is oxyalkylated alkylphenol-formaldehyde A mixture of glycol and thorium arylsulfonate is added to heavy aromatic naphtha. It consists of

When selecting the correct fuel/hydroemulsifier, operate the deposition control amount of fuel additives. The blended fuel repels water within 15-30 minutes of contact with the aqueous phase, i.e. It is important that the emulsion is essentially no longer in an emulsified state. Books commonly considered dispersants The fuel additive composition of the invention may also be used in gasoline compositions or water containing the additive composition. It also has a tendency to promote the formation of emulsions when in contact with. Comparison of demulsifiers At relatively low fuel concentrations, the demulsification of such emulsions is facilitated, thereby Helps clarify otherwise cloudy wet fuel. Demulsifier is also , can promote emulsification when used at concentrations higher than about 25 ppm. It is also important to keep in mind that

Therefore, the amount of those agents is determined by the physical amount of the fuel composition containing the fuel additive component of the present invention. /must be carefully tailored and adjusted to chemical properties. Many demulsifiers are other components of the fuel additive compositions of the present invention that satisfy the criteria of Compatibility standards are insufficient.

carrier fluid The carrier fluid used in the present invention does not significantly increase octane requirements. Contains non-volatile residues (NVR) or solvents of the fuel additive composition without contributing A chemically inert hydrocarbon-soluble liquid that substantially increases the liquid content It is le. The carrier fluid may be used, for example, as described in US Pat. 4. 191. Mineral oil and refined petroleum as described in Specification No. 537 , synthetic polyalkanes and alkenes, synthetic polyoxyalkanes derived from oils It can be a natural oil or a synthetic oil, such as kylene, etc. These carrier streams The body acts as a carrier for dispersants and detergents, and helps remove and retard deposits. It is thought to be long.

The carrier fluid used in the present invention may also be used in conjunction with other fuel additive compositions of the present invention. It must be possible to form a homogeneous mixture with the ingredients. suitable carry An example of a year fluid is San Francisco, California. Sieb on U. of San Francisco. S. A. Chevr on IJ. S. A. Inc. ) Chevron Neutral available from Oil (Chevron Neutral Oil) 5000R and Sheet There's 600P of Bron Neutral Oil.

fuel composition The fuel additive compositions of the present invention generally have a carbonized boiling point in the gasoline or diesel range. Used in hydrogen distillate fuel.

The correct concentration of this additive composition required to achieve the desired detergency and dispersibility. varies depending on the type of fuel used, the presence of other additives, etc. However, one Generally speaking, about 400 to 1,200 parts per million (p pm) of the fuel additive composition of the present invention is required to achieve best results. individual With respect to the ingredients, the fuel composition containing the homogeneous fuel additive composition of the present invention is Generally about 100-225 ppm of aminocarbamate dispersant, about 10-70 ppm pprn hydrocarbylamine cleaning agent for injectors, approximately 5-25 ppm Contains a demulsifier and about 250-800 ppm carrier fluid.

Deposition control fuel additive compositions of the present invention can be used at temperatures ranging from about 65.6 to 204.4°C. using an inert, stable lipophilic growing solvent that boils in the range of 150 to 400 degrees Fahrenheit. It can also be formulated as a concentrate. Aliphatic or aromatic hydrocarbon solvents, e.g. benzene, toluene, xylene or high-boiling aromatic compounds or aromatic thinners It is preferable to use Approximately 3 to 8 carbon sources in combination with a hydrocarbon solvent Fatty alcohols such as isopropanol, isobutyl carbino N-butanol, n-butanol, and the like are also suitable for use with the additive compositions of the present invention.

In fuel concentrates, the amount of the additive composition of the invention is usually at least 5% by weight and It generally does not exceed 50% by weight and is preferably 10-30% by weight.

In gasoline fuel, antiknock agents such as methylcyclopentadienyl ngantricarbonyl, tetramethyl or tetraethyl lead, tert-butylmethyl methyl peroxide and methanol, ethanol and methyl to monobutyl ether Pond fuel additives such as various oxygenators such as olefins may also be included. Also, Aryl halides, e.g. dichlorobenzene, alkyl halides, e.g. ethylene Lead scavengers such as ndipromide may also be included.

Additionally, antioxidants and metal deactivators may also be present.

In diesel fuel, additives such as pour point depressants, flow improvers, cetane improvers, etc. Other known additives may also be used.

The following examples are given to illustrate the invention. these The examples and explanations should not be construed as limiting the scope of the invention in any way. As described in Examples 6-8 of Hana Lewis U.S. Pat. No. 4,160,648. Dispersants useful in the present invention were prepared in a manner similar to that described above. However, Echire Diethylenetriamine was used instead of diamine. In this example, the text trapropenylphenol with butylene oxide, phosgene and diethylene tria high molecular weight tetrapropenyl poly(oxybutylene) by stepwise reaction with Aminocarbamate was obtained. In the following, this aminocarbamate is telamine (PEA) in Example 2 of U.S. Pat. No. 3,438,757. Injector in a manner similar to that described by Honnen in A cleaning agent (TD) was produced. In this example, a C2° point with a molecular weight of about 420 was used. Polyisobutyne is produced by stepwise reaction of lysobutyne with chlorine and ethylenediamine. An ethylenediamine adduct was produced.

In the following examples, Chevron neutral oil 500R and Chevron Neutral oil 600P was used as carrier fluid (CF). S Evron Neutral Oil 500R has a pour point of -12°C (maximum) and 40°C. It is a highly refined base oil with a viscosity of 98.6 cst at °C. S Evron Neutral Oil 600P has a pour point of -12.2°C (10°F) and a highly refined base oil with a viscosity of +29.5 cSt at 37.8°C. It is le.

The demulsifier (D) used in these examples to illustrate the invention was manufactured by the manufacturer. A commercially available product (Veterin, St. Louis, MO) named TORAD® T-326 It was a demulsifier from Lolite Co., Ltd., Toledolite Division). This thawing The oxidizing agent is an oxyalkylated alkylation agent in heavy aromatic naphtha (30-60% by weight). polyphenol-formaldehyde resin, polyoxyalkylene glycol and alcohol comprising a mixture of sodium lylsulfonate (1-5% by weight) . TORAD(R) T-326 has a flash point (SFCC) of 45.6°C 114°F ), pour point (ASTM D-97) -15°C (5°F), and 15.6°C ( It is reported to have a viscosity of 263 SUS at 60°F.

The method described in ASTM method D-1094 was used to test demulsibility. . Here, we will discuss the fuel phase, interface, transparency, and sustainability of the interfacial emulsion layer. evaluated. Tested on fuel additive compositions and evaluated mathematically on a scale of ■ to 4 did. A number “1” is the highest grade for clarity, and the durability of the interfacial emulsion layer. Regarding gender, "1" was set as the highest grade.

Sample 6A below, which is a typical example of a fuel additive composition of the present invention, was tested in both of these tests. It met the requirements for grade I.

A fuel additive composition was prepared. That is, 150 parts of the polyetheramine of Example J; 25 parts of the injector cleaning agent of Example 2, 12 parts of demulsifier, Chevron vine Hen) (Chevron 5olvent) 25 (This is Caliph t) Rainier C-9 obtained from Chevron U, S, A, Inc. of San Francisco, State. (a mixture of aromatic compounds for blending) 212 parts and Chevron Newt 450 parts of Ral Oil 500R (Example 3) was brought to room temperature in a 200ml flask. and mixed while stirring.

Sample 6A contained TORAD® T-326 (described in Example 4) as a demulsifier. It contained. Sample 6B contains L-1562 as a demulsifier There was. L-1562 was purchased from Vetrolite, St. Louis, MO. It is a commercially available demulsifier. Sample 6C of the third additive composition is an injector cleaning It contains oleylamine as an agent and is shown for comparison. Oreirua Min is a low molecular weight direct MC. The compatibility test used for II amine was the ASTM method. This was a modification of the method described in D-2273. However, these compositions Already a significant amount of diluent solvent (Chevron Solvent 25, for C-9 blends) mixture of aromatic compounds) was present, this test requires no further dilution. I went there. The test was divided into two parts.

In Bart A, the sample prepared by the method of Example 6 was heated to ambient temperature, i.e., room temperature (approximately 2 0-25°C) for 24 hours. Each sample was then visually inspected for the second phase. . If a second phase is observed, centrifuge the sample and measure the percent volume of the second phase. did. If a second phase was not observed, the Bart B of this test was performed.

In Bart B, the sample was cooled to 7.8°C (0'F) and heated at this temperature for 24 hours. Holds time. Each sample was then visually inspected for the second phase. Phase 2 was observed If so, the sample was centrifuged and the percent volume of the second phase was determined.

Second phase sediment after centrifugation – this can be a liquid, a solid or a combination of both. The results are shown in terms of volume percent. o, o o o exceeds capacity% The level of sediment (ie, second phase) produced is considered unacceptable.

The fuel additive composition of the present invention (Sample 6A) measured the second phase under these test conditions. It does not have a possible capacity percentage. However, L-1562 as a demulsifier (sample 6B), or as an injector cleaning agent. (Sample C), a strong and unacceptable level of the second phase was observed. It was done.

Sample 6A: 150 parts (7) PEA (Example 1) <0.005 <0.00 ID of 525 copies (Example 2) 212 parts Chevron Solvent 25 ■ 2 parts T-326 Sample 6B: 150 parts PEA (Example 1) 0.75 (comparison) 25 parts fD ( Example 2) 212 parts Chevron Solvent 2512 parts L-1562 Sample 6C: 150 parts (7) PEA (Example 1) <0.005 0.05 (ratio comparison) 25 parts of suleylamine 212 parts Chevron Solvent 25 ■ 2 parts T-326 For sample 6B, a liquid second phase was observed at ambient temperature. This is a fuel additive group Indicates incompatibility between the demulsifier and other ingredients of the composition.

Sample 6C containing oleylamine as an injector cleaner was ~17.8 After cooling to 'C (00F') and centrifuging, a small amount (0.05% by volume) of Showed an insoluble solid precipitate. Therefore, this sample has a sediment level of o, oos volume. It did not pass the standard that the amount should not exceed %.

When the fuel additive package of the present invention is added to unleaded regular gasoline, the fuel contains the following components: Added to have: 8A: 150 ppm PEA (Example) 25 ppm ID (Example 2) 450 ppm CF (Example 3, Chevron 600P) 12 pl) m D ( T-326) 8B: 150 ppm PEA (Example 1) 25 ppm ID (Example 2) 450 ppm CF (Example 3, Chevron 500R) 12 ppm D(T -326) Gasoline 1981 Pontiac 2.5 liter engine The method is to attach the engine to an engine test stand and run it for 90 hours. We tested its effectiveness in keeping the intake valve clean. This test is for light load driving It simulates a type of demanding field test characterized by conditions. be. The effectiveness of the additive package is determined by the intake valve build-up sedimentation obtained by the end of the test. Average the weight of the kimono and compare these results using the same test conditions and additive-free fuel. Determine by comparing with the obtained results. Perfecting the intake system cleanliness retention performance A good fuel additive package can typically be added to the base gasoline Reduces intake valve deposits.

Using the above test conditions, unadditive base gasoline averages + , o9o milligrams of deposit were formed. Chevron neutral oil 6 00P, the same containing the fuel additive package of Example 8A. Gasoline deposits averaged 23 milligrams per intake valve. Compare the above Additive fuel containing base fuel and Chevron neutral oil 500R ( Example 8B), an average of 299 milligrams of intake valve deposits were observed. Ta. These results are summarized below.

Fuel Blend: Contains Average Deposit Weight (for base fuel without additives) 1090mg8A 23mg 8B 299mg For both 5A and 8B, the average deposit weight is significantly lower than for base fuel. This shows the effectiveness of the fuel additive composition of the present invention.

Example 9 Octane Requirement Increase Test This test applies to engines operated on gasoline where gasoline additives may be present. It measures the potential for disturbing the gin's octane requirements. time has passed If the fuel is too hot, higher octane gasoline will run into the engine due to deposit build-up in the combustion chamber. required to minimize knock conditions. Additive-free gasoline increases to begin testing to minimize possible engine knock conditions. Sedimentation typically requires a fuel with an octane rating 4 higher than the initial fuel used. Give a certain reference line level of kimono. Gasoline additives contribute to this problem to varying degrees. The magnitude of this contribution can be determined by comparison with engine tests using additive fuel. It can be measured. The difference in ORI observed between tests was due to engine knock With that additional increment of increased octane required to further minimize the Yes, commonly referred to as increased octane requirements due to the gasoline additive package itself. be done.

This value is typically referred to as the "additive ORI value."

In this method, the engine is mounted on an engine stand and tested under test conditions and engine operation. 1975 Toyota with a control system that carefully adjusts rotation cycles A 2.2 liter engine is used. First, the engine burns relatively cleanly, Run for 15 hours on alkylate fuel without additives. At this point, Octa Measure the fuel price requirement and change the fuel to 70% unleaded regular gasoline and FCC heavy. Replace with a mixture of 30% gasoline. FCC heavy gasoline composition test Used to increase the rate of deposit accumulation in the combustion chamber during stages. 110 hours After additional engine runs, final octane requirement measurements are taken.

When tested in this manner, the fuel additive package of the present invention yields additive-free fuel. 1/2 octane higher than the octane requirement observed for (Test 9A). This increase is due to the molecular weight and the average increase of 100 carbon atoms. was reacted stepwise with chlorine and ethylenediamine, with an average molecular weight of about 1450. heavy polybutene amines and large amounts of carrier The increase observed for a commercial gasoline additive package consisting of 9B).

Base: No additives 4. O.

Test 9A.

isoppm of PEA (Example 1) 4.5 0.525ppm of [D] (Example 1) Example 2) 250ppm + 7) Heavy Bolibudde 7T Mi 7 7.0 3.0 engraving (changed in content none) Summary book Next ingredient.

(a) contains at least one basic nitrogen atom and has an average molecular weight of about too much Up to about 3000 hydrocarbyl poly A dispersant consisting of; (b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to Approximately 700 branched-chain human ``locarbylamines'' whose hydrocarbyl 06 The hydrocarbylamine is derived from a polymer of lefin. Injection cleaning agent consisting of: (C) a fuel demulsifier that is homogeneous with the other components of the final fuel additive composition; and (d) A homogeneous fuel additive composition comprising a natural or synthetic carrier fluid.

Procedural amendment (voluntary) 1-Display of incident 2. Name of the invention fuel additive composition Full name (name) Chevron Research and Technology Company 4, Agent 6 - Number of claims increased by amendment 7-Subject of correction Description and claims translation international search report I inner 1erwm*-^-hem cell-1 fist r/blind+CQ+/MO-1

Claims (16)

[Claims] 1. The following ingredients: (a) has at least one basic nitrogen atom and has an average molecular weight of about 1000 to Contains approximately 3000 hydrocarbyl poly(oxyalkylene) aminocarbamates. A dispersant consisting of; (b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to about 700 branched chain hydrocarbyl amines, the hydrocarbyl moiety of which is C2 The hydrocarbylamine is derived from a polymer of ~C8 olefins. An injection cleaning agent comprising; (c) a fuel demulsifier that is homogeneous with the other components of the final fuel additive composition; and (d) carrier fluid, natural or synthetic; A homogeneous fuel additive composition comprising: 2. The hydrocarbyl group in component (a) contains from 1 to about 30 carbon atoms. The fuel additive composition according to claim 1, which is 3. Claims wherein the hydrocarbyl group in component (a) is an alkylphenyl group A fuel additive composition according to paragraph 1. 4. Claims in which the alkyl moiety in the alkylphenyl group is tetrapropenyl 3. The fuel additive composition according to item 3. 5. The amine moiety of the aminocarbamate has 2 to 12 amine nitrogen atoms and 2 to 12 amine nitrogen atoms. Claim No. 1, which is derived from a polyamine having 40 carbon atoms. The fuel additive composition according to item 1. 6. The polyamine has 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms. The fuel additive set according to claim 5, which is a polyalkylene polyamine that A product. 7. Polyalkylene polyamines include ethylene diamine, propylene diamine, diene selected from the group consisting of thylenetriamine and dipropylenetriamine; A fuel additive composition according to claim 6. 8. The poly(oxyalkylene) part of component (a) is C2-C5 oxyalkylene A fuel additive composition according to claim 1, which is derived from the unit. 9. Hydrocarbyl poly(oxyalkylene) aminocarbamate of component (a) is an alkylphenyl poly(oxybutylene) aminocarbamate, and its alkyl phenyl poly(oxybutylene) aminocarbamate The amine moiety is derived from ethylenediamine or diethylenetriamine. The fuel additive composition according to claim 1. 10. The branched hydrocarbyl moiety of component (b) is polypropenyl or polyisobutyl The fuel additive composition of claim 1, wherein the fuel additive composition is Tenyl. 11. The amine group of the branched chain hydrocarbylamine of component (b) is ethylenediamine. , diethylenetriamine, triethylenetetramine and tetraethylenepentamine The fuel additive according to claim 1, which is selected from the group consisting of: Composition. 12. The branched chain hydrocarbylamine of component (b) is polyisobutenyl ethylenedi The fuel additive composition of claim 1, which is an amine. 13. Component (a) is alkylphenyl poly(oxybutylene) aminocarbame The amine moiety is derived from ethylenediamine or diethylenetriamine. and component (b) is polyisobutenylethylenediamine. A fuel additive composition according to claim 1. 14. Hydrocarbons boiling in the range of gasoline or diesel, as well as approximately 400 parts to about 1,200 parts of the following ingredients: (a) has at least one basic nitrogen atom and has an average molecular weight of about 1000 to Contains approximately 3000 hydrocarbyl poly(oxyalkylene) aminocarbamates. A dispersant consisting of; (b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to about 700 branched chain hydrocarbyl amines, the hydrocarbyl moiety of which is C2 - said hydrocarbylamine derived from a polymer of C6 olefins An injector cleaning agent comprising; (c) a fuel demulsifier that is homogeneous with the other components of the fuel additive composition; and (d) carrier fluid, natural or synthetic; A fuel composition comprising a homogeneous fuel additive composition comprising: 15. about 100 to 225 ppm of component (a) dispersant; about 10 to 70 ppm of component (a); component (b) of an injector cleaning agent; component (c) of a demulsifier of about 5 to 25 ppm; and about 250 to 800 ppm of component (d) carrier fluid. The fuel composition according to range item 14. Inert boiling between 150 and 400 degrees Fahrenheit and about 5 to 50% by weight of the following ingredients: (a) has at least one basic nitrogen atom and has an average molecular weight of about 1000 to 3; Contains 000 hydrocarbyl poly(oxyalkylene) aminocarbamates Dispersant consisting of: (b) has at least one basic nitrogen atom and has an average molecular weight of about 300 to 70; 0 branched chain hydrocarbyl amine, the hydrocarbyl moiety of which is C2-C The hydrocarbylamine is derived from a polymer of 6 olefins. (c) homogeneous with the other components of the fuel additive composition; certain fuel demulsifiers; and (d) carrier fluid, natural or synthetic; A fuel concentrate comprising a homogeneous fuel additive composition comprising: