JP2854973B2 - Fuel additive composition - Google Patents

Abstract

A homogeneous fuel additive composition which comprises: (a) a dispersant comprising a hydrocarbyl poly (oxyalkylene) aminocarbamate having at least one basic nitrogen atom and an average molecular weight of about 1000 to about 3000; (b) an injection detergent comprising a branched-chain hydrocarbyl amine having at least one basic nitrogen atom and an average molecular weight of about 300 to about 700, wherein the hydrocarbyl moiety is derived from polymers of C2 to C6 olefins; (c) a fuel demulsifier which is homogeneous with the other components of said fuel additive composition; and (d) a natural or synthetic carrier fluid.

Description

DETAILED DESCRIPTION OF THE INVENTION Hydrocarbon fuels inherently contain a large number of deposit-forming substances. These materials, when used in internal combustion engines, tend to form deposits in and around the narrow area of the internal combustion engine where the fuel comes into contact. Typical areas where deposit formation is generally and sometimes significantly overburdened are carburetor air bleeds, throttle bodies and venturis, engine intake valves and intakes, fuel injection nozzles, cylinder beds and piston top combustion chambers. Surface.

Deposits adversely affect the operation of vehicles using hydrocarbon fuels. For example, deposits on the carburetor throttle body and venturi increase the fuel to air ratio of the gas mixture to the combustion chamber, thereby increasing the amount of unburned hydrocarbons and carbon monoxide exhausted from the combustion chamber. A high fuel-to-air ratio also reduces the mileage per gas achievable by the vehicle.

Heavy enough deposits on the intake valves of the engine limit the flow of the gas mixture into the combustion chamber. This limitation causes the engine to run out of air and fuel and reduces power. Deposits on the intake valve also increase the likelihood of valve failure due to combustion and improper valve seat fixation. In addition, these deposits break off into the combustion chamber, possibly with a piston top,
Mechanical damage to piston rings, cylinder heads, etc.

It has long been known that the formation of these deposits can not only be removed but also suppressed by incorporating an active detergent into the fuel. These cleaning agents function to clean these areas where harmful deposits are likely to deposit, thereby increasing the performance and life of the engine.

The first generation of fuel additives consisted of detergents that help maintain the cleanliness of important carburetor elements. These early fuel additives can be used in small doses, typically between 15 and
Typically, a dose in the range of 30 ppm was used.
Unfortunately, these small doses of the additive provided little control over deposition in other parts of the fuel engine.

The next generation of fuel additives generally improved deposition control in the intake system, including the intake manifold hot spots, runners, intake valves and intake valves. The degree of deposition control typically depends on the additive dose, usually
It was adjusted by controlling in the range of 70 to 2,000 ppm. However, as the additive dose went up to higher levels, the buildup of deposits in the combustion chamber became a serious problem for the reasons identified below.

In recent years unleaded gasoline has become widely used, which further complicates the use of detergent-type gasoline additives. Gasoline with sufficient octane number to prevent knocking and associated damage in automotive engines that require the use of unleaded gasoline (to prevent inactivation of catalytic converters used to reduce emissions) It proved difficult to provide. This problem is caused by the increasing octane requirement increas, referred to herein as "ORI".
e), the increase being the result of deposits formed by the use of commercial gasoline.

The basis of the ORI problem is as follows: Each engine, when it is new and / or after running, pings
g) and / or require a fuel with a certain minimum octane number to operate well without knocking.
This minimum octane requirement increases as the engine is run on gasoline. This is obviously caused by the formation of deposits in the combustion chamber. In most cases, running the engine on the same fuel for an extended period of time will reach its equilibrium. Typically, equilibrium is reached after driving a car for 5,000 to 15,000 miles.

The increase in octane requirements in certain engines using commercial gasoline will vary from 4-6 octane units to as high as 12-15 octane units at equilibrium, depending on gasoline composition, engine design and type of operation. The significance of this problem is thus clear. A typical car with a research octane requirement of 85, when it is a new car, requires gasoline with a research octane number of 97 for proper operation after several months of driving, but unleaded gasoline with that octane number almost never Not available. ORI
The problem also exists to some extent with engines that operate on leaded fuel. U.S. Patent Nos. 3,144,311 and 3,146,2
No. 03 and 4,247,301 disclose lead-containing fuel compositions having reduced ORI properties.

The ORI problem is complicated by the fact that the most common way to upgrade the octane rating of unleaded gasoline is to increase its aromatic content. These aromatics, however, ultimately cause a greater increase in octane number requirements. In addition, some of the nitrogen-containing compounds and their mineral or polymer carriers currently used as deposition control additives also contribute significantly to the ORI problem in engines using lead-free fuels.

Accordingly, it is particularly desirable to provide a deposition control additive that operates at a dose sufficient to effectively control deposits in the intake system of the engine without significantly contributing to the ORI problem. Hydrocarbyl poly (oxyalkylene) aminocarbamate OR-derived derivatives
I A commercially successful fuel additive that controls without significantly contributing to the problem. However, these additives are relatively expensive, which hinders their use at high concentrations.

At economic fuel concentrations, hydrocarbyl poly (oxyalkylene) amino carbamates are not very effective at controlling deposits in injectors or carburetors of modern combustion engines. The performance of these engines, including the fuel injection fuel delivery system, can be substantially impaired by relatively small amounts of deposits.

On the other hand, it is known that hydrocarbylamine-based and polyamine-based detergents in component amounts effectively control deposits in the injector. These amine-based detergents are similar to those described above used to keep the carburetor clean. However, these detergents are used at fuel concentrations ranging from 40 to 70 ppm to control deposits on the injector. It is now known that such high doses of injector cleaner have a negative effect on the intake valves of the engine and on the control of deposits in the combustion chamber.

An additional problem with certain low molecular weight hydrocarbylamine and polyamine based detergents having primary and secondary amine functionality is that when the amine is exposed to carbon dioxide, such as when exposed to carbon dioxide in air, Is to form a precipitate. This precipitate is believed to be a carbamic acid adduct formed by the reaction of the primary or secondary amine with carbon dioxide. Whatever the chemical structure, the formation of such a precipitate is undesirable for the reasons explained below.

Yet another problem associated with certain low molecular weight amines, especially those having polar substituents, such as hydroxy groups, is that they have a high degree of water solubility, and thus, when contacted with water, the amine is converted from the hydrocarbon phase into water. This means that it can be completely extracted into the phase. As a result, the effectiveness of such amines in hydrocarbon fuels will be reduced.

In this regard, U.S. Pat. No. 4,810,263 to Zimmerman et al. Discloses an additive package for reducing and / or preventing pollution in fuel injected multi-port engines. The additive package comprises one or two selected from amine oxides, such as bis (2-hydroxyethyl) cocamine oxide, and the reaction product of a fatty acid alkylamine, and a solution of an oxyalkylated alkylphenol formaldehyde resin and polyglycol. It contains a demulsifier consisting of one or more demulsifiers. U.S. Pat. No. 4,836,829 to Zimmerman et al. Discloses a similar additive package containing a tertiary amine, such as bis (2-hydroxyethyl) cocamine, preferably in combination with an amine oxide, and a demulsifier. Is done. The amine oxide typically contains water that is present from its manufacturing process and is difficult to remove completely, as seen in US Pat. No. 4,810,263. As a result, the amine oxide is commercially available as an isopropyl alcohol solution containing 6-8% by weight of water.

Mineral oil-based carriers are often used with either amine-based detergents or hydrocarbyl poly (oxyalkylene) aminocarbamate-based dispersants to help remove or prevent deposits. However, neither addition of mineral oil-based carriers provides complete intake system deposition control for either group of fuel additives.

Accordingly, an additive for controlling deposition of an intake valve and a combustion chamber, for example, a hydrocarbyl poly (oxyalkylene) aminocarbamate-based dispersant, is used as a cleaning agent for an injector,
For example, in combination with low molecular weight amines or polyamines and an effective amount of a carrier fluid, maximizes effective control of deposits throughout the intake system and combustion chamber of the engine, and is itself a major solution to the increasing octane requirement. It would be particularly desirable to provide a multi-component, multi-functional fuel additive package that does not contribute.

The selection of components for a multi-component, multi-functional deposition control fuel additive composition is not straightforward. The composition should provide effective deposition control at economical additive levels and with additives that do not contribute to ORI. Also, the composition remains homogeneous in all field conditions if it should reliably deliver the expected performance of deposition control when it is blended with the fuel and when the engine is actually running. That is, a single liquid phase is essential.

It is important to maintain a single liquid phase in providing an effective fuel additive composition. Generally, once the additive composition has been distributed in the fuel field, there is no practical means of rehomogenizing it. If a large amount of the additive composition separates into two or more phases as a result of component incompatibility, neither phase contains an effective combination of the components intended for the fuel. Therefore, the overall deposition control performance of this fuel is severely degraded. Moreover, the additive composition delivered to the fuel is not constant.

Phase separation of an incompatible composition can take many forms. Typically, phase separation first appears as cloudiness. This clouding will eventually settle out and break out either above or below depending on the relative densities of the two phases. Thus, for example, as the level of the additive in the storage tank is withdrawn, the interface between the phases may shift below the draw point of the liquid, at which point the additive composition flowing into the fuel will probably change drastically. I do.

Phase separation also causes significant problems for additive distribution systems that distribute the additive composition to the fuel. If phase separation involves two liquid phases, the heavier phase collects at the bottom of the additive storage tank and at a lower point in the additive delivery line. This requires expensive and inconvenient periodic cleaning of the additive distribution device.

If phase separation involves solids separating from large amounts of the liquid additive composition, the effect is even more significant and appears immediately.
Virtually all additive injection systems are equipped with a fine mesh filter to protect the injection pump valves and seals. The solid phase rapidly clogs these filters and renders the injector inoperable, so it may be necessary to clean the filters before restarting the injector. Another solid phase would also require periodic cleaning of the additive storage tank. Thus, the criticality of a homogeneous additive composition is evident.

It is generally believed that it is advantageous to include a small amount of fuel / water demulsifying material in the fuel blend of the additive composition. Demulsifiers must exhibit demulsifying properties when used at relatively low levels in motor fuels, for example at levels of 5 to 25 parts per million. However, such substances, even at low dosages, are, in certain instances,
It has been observed that the additive composition can have a negative effect on the deposition control. Therefore, it is desirable to select a demulsifier that does not exhibit this negative effect. In addition, it is important that the demulsifier remain homogeneous with the additive composition for the reasons described above.

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

Related Art U.S. Pat. Nos. 4,160,648 and 4,191,537 disclose hydrocarbyl poly (oxyalkylene) aminocarbamates as fuel additives. The use of fuel soluble carrier oils, as well as demulsifiers, with hydrocarbyl poly (oxyalkylene) amino carbamates is also disclosed.

The use of hydrocarbylamines and hydrocarbylpolyamines as fuel additives is disclosed in the following U.S. Patents: 3,438,757, 3,565,804
No. 3,574,576, No. 3,898,056 and No. 3,960,
No. 515.

U.S. Pat. Nos. 3,898,056 and 3,960,515 disclose mixtures of high and low molecular weight hydrocarbylamines used as detergents and dispersants at low concentrations in fuels. High molecular weight hydrocarbylamines are those having at least one hydrocarbyl group having a molecular weight of about 1,900 to 5,000, while low molecular weight hydrocarbylamines are those having at least one hydrocarbyl group having a molecular weight of about 300 to 600. The weight ratio of low molecular weight amine to high molecular weight amine in the mixture is maintained at about 0.5: 1 to 5: 1.

These references disclose hydrocarbyl poly (oxyalkylene) amino carbamates useful as dispersants and hydrocarbylamines and polyamines useful as detergents, but they disclose OR concentrations when mixed with fuel at low concentrations.
No one teaches a homogeneous additive composition comprising a dispersant, a detergent, a carrier oil and a demulsifier that provides effective deposition control throughout the intake system while minimizing the contribution to the I problem. .

SUMMARY OF THE INVENTION The present invention provides a dispersant comprising: (a) a hydrocarbyl poly (oxyalkylene) aminocarbamate having at least one basic nitrogen atom and having an average molecular weight of about 1,000 to about 3,000; b) at least one basic nitrogen atom, a branched-chain hydrocarbyl amine of about 300 to about 700 average molecular weight, in which the hydrocarbyl moiety is derived from C ₂ -C ₆ olefin polymer A detergent for injectors comprising hydrocarbylamine; (c) a fuel demulsifier which is homogeneous with other components of the final fuel additive composition; and (d) a natural or synthetic carrier fluid. It provides a homogeneous fuel additive composition.

The present invention further provides a fuel composition comprising a hydrocarbon boiling in the range of gasoline or diesel and about 400 to 1,200 parts per million of the above homogeneous fuel additive composition.

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

Among other factors, the present invention relates to a combustion chamber depletion effect wherein a unique combination of the dispersants, low molecular weight injector cleaners, demulsifiers and carrier fluids described herein correlates with ORI. It is based on the surprising finding that it provides safe deposit control of the intake system while minimizing sexual deposits.

In addition, the use of low molecular weight branched-chain hydrocarbylamines as injector cleaners avoids the precipitation problems associated with known amine cleaners, such as oleylamine.

DETAILED DESCRIPTION OF THE INVENTION In summary, the present invention is able to provide complete deposition control of gasoline intake systems whether conventional fuel additives, either alone or in typical use of rich combinations It addresses the problem associated with the fact that nothing is. The present invention demonstrates a new compounding technique that provides maximum deposition control in each deposition-forming critical region while minimizing the dose of each critical component. As a result, it is now possible to minimize the negative impact of individual components on the overall deposition control performance of the intake system and the combustion chamber.

The present invention describes a fuel additive composition that provides a homogeneous mixture of a deposition control additive and a demulsifier that is compatible with carrier fluids and oils. Here, the deposition control additive and the carrier fluid are in individual proportions that are significantly lower than the levels historically found to maintain adequate intake system deposition control in the respective area of effectiveness.

Accordingly, the novel fuel additive composition of the present invention comprises the following components: (a) a hydrocarbyl poly (oxyalkylene) amino carbamate having at least one basic nitrogen atom and having an average molecular weight of about 1,000 to about 3,000. dispersing agent consisting of; (b) having an at least one basic nitrogen atom, a branched-chain hydrocarbyl amine having an average molecular weight from about 300 to about 700, from the hydrocarbyl moiety is C ₂ -C ₆ olefin polymer An injector detergent comprising the derived hydrocarbylamine; (c) a fuel demulsifier which is homogeneous with the other components of the final fuel additive composition; and (d) a natural or synthetic carrier fluid. A homogeneous mixture consisting of

Generally, the homogeneous fuel additive composition of the present invention will comprise from about 10 to 70
By weight of the aminocarbamate-based dispersant, about 1-10% by weight of the hydrocarbylamine-based injector cleaner, about 0.5-5% by weight of the fuel demulsifier and about 25-8%
Contains 0% by weight of the above carrier fluid. Although the fuel additive composition of the present invention can be used neat, it is often desirable to dilute the composition with an inert solvent or diluent to a dilution of about 50% or less.

Dispersant The dispersant used in the homogeneous fuel additive composition of the present invention is a hydrocarbyl poly (oxyalkylene) aminocarbamate having at least one basic nitrogen atom and having an average molecular weight of about 1,000 to 3,000. Thus, it can be said that the dispersant used comprises a poly (oxyalkylene) component, an amine component and a carbamate connecting group.

A. Poly (oxyalkylene) Component The hydrocarbyl-terminated poly (oxyalkylene) polymer used in making the carbamates of the present invention is a monohydroxy polyether or polyalkylene glycol monocarbyl ether, ie, "capped".
A monohydroxy compound often referred to as poly (oxyalkylene) glycol, such as an alcohol,
It should be distinguished from poly (oxyalkylene) glycols (diols) or polyols that are not terminated with hydrocarbyl, i.e. uncapped.
Hydrocarbyl-terminated poly (oxyalkylene) alcohols are prepared by adding lower alkylene oxides, such as oxirane, ethylene oxide, propylene oxide, butylene oxide, etc. under hydroxy compound ROH polymerization conditions. However, in the above formula, R
Is a hydrocarbyl group that caps the poly (oxyalkylene) chain. In the poly (oxyalkylene) component used in the present invention, the group R generally contains from 1 to about 30 carbon atoms, preferably from 2 to about 20 carbon atoms, so that it is aliphatic or aromatic, ie, alkyl. Group is about 1
Preference is given to alkyl or alkylphenyl, which is straight-chain or branched having 24 carbon atoms. More preferably, R is alkylphenyl wherein the alkyl group is of a branched chain having 12 carbon atoms derived from a tetramer of propylene, commonly referred to as tetrapropenyl. The oxyalkylene units in the poly (oxyalkylene) component preferably have 2 to 5 carbon atoms,
One or more units of larger carbon atoms may be present. The poly (oxyalkylene) component used in the present invention is more fully described and exemplified in US Pat. No. 4,191,537, the disclosure of which is incorporated herein by reference.

Although the hydrocarbyl groups attached to the hydrocarbyl poly (oxyalkylene) component preferably contain from 1 to about 30 carbon atoms, longer hydrocarbyl groups, especially long chain alkylphenyl groups, may be used.

For example, alkylphenyl poly (oxyalkylene) amino carbamates wherein the alkyl group has at least 40 carbon atoms, as described in U.S. Pat. No. 4,881,945 to Bubkley, are also contemplated for use in the present invention. Things. This U.S. Pat.
The alkylphenyl group attached to the amino carbamate in the specification of 1,945 preferably contains an alkyl group having 50 to 200 carbon atoms, and contains an alkyl group having 60 to 100 carbon atoms. Is more preferred. The disclosure of U.S. Pat. No. 4,881,945 is incorporated herein by reference.

B. Amine Component The amine portion of the hydrocarbyl-terminated poly (oxyalkylene) amino carbamate is preferably derived from a polyamine having 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. The polyamine is preferably reacted with a hydrocarbyl poly (oxyalkylene) chloroformate to produce a hydrocarbyl poly (oxyalkylene) amino carbamate fuel additive which has utility within the scope of the present invention. Chloroformate is itself derived from a hydrocarbyl poly (oxyalkylene) alcohol by reaction with phosgene. Polyamines, including diamines, provide product poly (oxyalkylene) amino carbamates having an average of at least about one basic nitrogen atom per carbamate molecule, i.e., a nitrogen atom that can be titrated with a strong acid. Polyamine is about 1: 1
Preferably, it has a carbon to nitrogen ratio of from about 10: 1. Polyamines include hydrogen, hydrocarbyl groups having 1 to about 10 carbon atoms, acyl groups having 2 to about 10 carbon atoms, and monoketones, monohydroxy, mononitro, of hydrocarbyl groups having 1 to 10 carbon atoms. It may be substituted with a substituent selected from monocyano, alkyl and alkoxy derivatives. Preferably, at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen atom. The polyamine component used in the present invention is more fully described and exemplified in US Pat. No. 4,191,537.

The hydrocarbyl used in describing the hydrocarbyl (oxyalkylene) component and the amine component used in the present invention means an organic group composed of carbon and hydrogen, which may be aliphatic, cycloaliphatic, aromatic or a combination thereof. , For example, aralkyl. Preferably, the hydrocarbyl group is relatively free of aliphatic unsaturation, ie, ethylenic and acetylenic unsaturation, especially acetylenic unsaturation. Further preferred polyamines that have utility within the scope of the present invention are polyalkylene polyamines, including alkylenediamines, and also substituted alkylene polyamines, including alkyl and hydroxyalkyl substituted polyalkylene polyamines. Preferably,
Preferably, the alkylene group contains 2-6 carbon atoms, with 2-3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, di (trimethylene) triamine, dipropylenetriamine, tetraethylenepentamine, and the like. Among the polyalkylene polyamines, polyethylene polyamines and polypropylene polypropylenes containing 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms are particularly preferred, and especially lower polyalkylene polyamines such as ethylene diamine, diethylene triamine, propylene diamine, diamine Most preferred is propylene triamine and the like.

C. Amino Carbamate The poly (oxyalkylene) amino carbamate fuel additive used in the compositions of the present invention is a carbamate linkage of the amine component and the poly (oxyalkylene) component together, ie, Obtained by bonding via However,
The oxygen in the formula can be regarded as the oxygen of the terminal hydroxyl group of the poly (oxyalkylene) alcohol component, and the carbonyl group -C (O)-is preferably provided by a coupling agent such as phosgene. In a preferred process, the hydrocarbyl poly (oxyalkylene) alcohol is reacted with phosgene to form a chloroformate, and the chloroformate is reacted with a polyamine. Carbamate linkages are formed as the poly (oxyalkylene) chain is attached to the nitrogen of the polyamine via the oxycarbonyl group of the chloroformate. Amino carbamates have at least one hydrocarbyl poly (oxyalkylene) polymer chain linked to the polyamine via an oxycarbonyl group since the polyamine capable of reacting with the chloroformate can have one or more nitrogen atoms. The carbamate may have one, two, three or more such polymer chains. The product hydrocarbyl poly (oxyalkylene) aminocarbamate has on average about one poly (oxyalkylene) chain per molecule (ie, is a monocarbamate).
However, the reaction route may result in a mixture in which the polyamine containing some reactive nitrogen atoms has a significant amount of di- or tri- or higher poly (oxyalkylene) chain substitution. Particularly preferred amino carbamates are alkyl phenyl poly (oxyalkylene) amino carbamates where the amine moiety is derived from ethylene diamine or diethylene triamine. Synthetic methods, preparative methods and other properties of the aminocarbamates used in the present invention that avoid higher degrees of substitution are more fully described and exemplified in US Pat. No. 4,191,537.

Injector Detergent The injector detergent used in the homogeneous fuel additive composition of the present invention is a branched hydrocarbylamine having at least one basic nitrogen atom and having an average molecular weight of about 300 to about 700. And the hydrocarbyl moiety is
A C ₂ -C ₆ olefin branched hydrocarbyl amines is derived from a polymer.

In injector amine detergents, the branched hydrocarbyl groups are usually produced by polymerizing an olefin having 2 to 6 carbon atoms (where ethylene is combined with another olefin to give a branch). Copolymerized). Branched hydrocarbyl groups generally have at least one per six carbon atoms, preferably at least one per four carbon atoms, and more preferably two per carbon atom along the chain. It has at least one branch. Preferred branched hydrocarbyl groups are polypropylene and polyisobutylene. These branches are usually of 1 to 2 carbon atoms, preferably of 1 carbon atom, ie methyl. Generally, branched hydrocarbyl groups will have about 20-40 carbon atoms.

In most cases, a branched hydrocarbylamine is not a pure single product, but a mixture of compounds having a certain average molecular weight. The molecular weight range is usually relatively narrow, with peaks near the specified molecular weight.

The amino component of the branched hydrocarbylamine can be either a monoamine or a polyamine. Monoamino or polyamino components have 1 to 10 nitrogen atoms and 2 to 40
A broad group of amines having carbon atoms and a carbon to nitrogen ratio of 1: 1 to 10: 1. In most cases, the amine component is not a pure single product, but a mixture of compounds, the majority of which are the indicated amines. In the case of more complex polyamines, their composition is an amine mixture containing the specified compound as the main product and small amounts of analogous compounds.

When the amine component is a polyamine, it is preferably a polyalkylene polyamine, including an alkylenediamine. Preferably, the alkylene group contains 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.
Examples of such polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

A particularly preferred branched hydrocarbylamine is polyisobutenylethylenediamine.

The branched-chain hydrocarbylamine detergents for injectors used in the fuel additive compositions of the present invention are prepared by conventional methods known in the art. Such branched hydrocarbylamines and their preparation are described in U.S. Patent Nos. 3,438,757, 3,565,804,
Nos. 574,576, 3,848,056 and 3,960,515. The disclosures of these specifications are cited and referred to herein.

Demulsifier The demulsifier used in the fuel additive composition of the present invention is:
When used at relatively low concentrations in gasoline compositions, the emulsified water can be effectively removed from large quantities of hydrocarbons by statically separating it in a stationary storage tank with the aid of gravity. It is a chemical agent that promotes rapid coalescing to the point where possible. The demulsifier is often a mixture of several chemical agents that contain the desired demulsifying properties in the right combination. These agents are typically, but not limited to, selected from alkylphenol resins, fluids based on polyoxyalkylenes, alkylarylsulfonates, derivatives of fatty acids, and the like.
One preferred demulsifier for use in the compositions of the present invention is St. Louis, Missouri.
Tolad® T-326, a demulsifier commercially available from Petrolite Corporation, Tretolite Division, Inc.
Which comprises a mixture of oxyalkylated alkylphenol-formaldehyde resin, polyoxyalkylene glycol and sodium aryl sulfonate in heavy aromatic naphtha.

In selecting the right fuel / water demulsifier, the fuel blended with an effective deposition control amount of fuel additive repels water within 15-30 minutes upon contact with the aqueous phase, ie, is essentially not emulsified This is very important. Fuel additive compositions of the present invention, which are generally regarded as dispersants, also have a tendency to promote the formation of emulsions when gasoline compositions containing the additive composition come into contact with water. Demulsifiers, at relatively low fuel concentrations, facilitate demulsification of such emulsions, thereby helping to clarify otherwise cloudy wet fuels. It is important to note that demulsifiers can also promote emulsification when used at concentrations higher than about 25 ppm. Therefore, their amounts must be carefully adjusted and adjusted to the physical / chemical properties of the fuel composition containing the fuel additive component of the present invention. Although many demulsifiers satisfy this criterion, the criteria for compatibility with the other components of the fuel additive composition of the present invention are nevertheless insufficient.

Carrier Fluid The carrier fluid used in the present invention does not significantly contribute to the increase in octane number requirements, but a chemical which substantially increases the non-volatile residue (NVR) or solvent-free liquid content of the fuel additive composition. Inactive hydrocarbon soluble liquid vehicle. Carrier fluids include, for example, mineral oils, refined petroleum, synthetic polyalkanes and alkenes, synthetic polyoxyalkylenes derived from oils, as described in US Pat. No. 4,191,537 to Lewis. And the like can be natural or synthetic oils. It is believed that these carrier fluids act as carriers for the dispersant and detergent, and help remove and delay deposits.

The carrier fluid used in the present invention must also be capable of forming a homogeneous mixture with the other components of the fuel additive composition of the present invention. Examples of suitable carrier fluids include Chevron USA, Inc. (C San Francisco, California).
Hevron USA Inc.) available from Chevron Neutral Oil 500R and Chevron Neutral Oil 600P.

Fuel Composition The fuel additive composition of the present invention is generally used in hydrocarbon distillate fuels boiling in the gasoline or diesel range. The proper concentration of this additive composition required to achieve the desired detergency and dispersibility will vary depending on the type of fuel used, the presence of other additives, and the like. However, in general, about 400 to 1,2 per million parts in base fuel
00 parts (ppm) of the fuel additive composition of the present invention are required to achieve the best results. With respect to the individual components, the fuel composition containing the homogeneous fuel additive composition of the present invention generally comprises from about 100 to 225 ppm of the aminocarbamate dispersant, from about 10 to about 10 ppm.
It contains 〜70 ppm of hydrocarbylamine detergent for injectors, about 5 to 25 ppm of demulsifier and about 250 to 800 ppm of carrier fluid.

The deposition control fuel additive composition of the present invention comprises about 6
It can also be formulated as a concentrate using an inert and stable lipophilic organic solvent that boils in the range of 5.6-204.4 ° C (150-400 ° F). It is preferred to use an aliphatic or aromatic hydrocarbon solvent such as benzene, toluene, xylene or a high boiling aromatic compound or aromatic thinner. Aliphatic alcohols having about 3 to 8 carbon atoms in combination with hydrocarbon solvents, such as isopropanol, isobutylcarbinol, 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 generally does not exceed 50% by weight, and is preferably 10 to 30% by weight.

In gasoline fuels, antiknock agents such as methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, tert-butyl methyl peroxide, and methanol, ethanol and methyl t
Other fuel additives such as various oxygenates such as -butyl ether may also be included. Also, a lead scavenger such as an aryl halide, for example, dichlorobenzene, an alkyl halide, for example, ethylene dibromide may be included. In addition, antioxidants and metal deactivators can be present.

In diesel fuel, other well-known additives such as pour point depressants, flow improvers, cetane improvers and the like can be used.

The following examples are provided to illustrate the invention. These examples and descriptions should not be construed as limiting the scope of the invention in any way.

EXAMPLES Example 1 Preparation of Amino Carbamate Dispersants Useful in the Invention Examples 6 to 6 of Lewis U.S. Pat. No. 4,160,648.
In a manner similar to that described in Example 8, a dispersant useful in the present invention was prepared. However, diethylenetriamine was used instead of ethylenediamine. In this example, tetrapropenyl phenol is converted to butylene oxide,
High molecular weight tetrapropenyl poly (oxybutylene) by stepwise reaction with phosgene and diethylenetriamine
The amino carbamate was obtained. Hereinafter, this amino carbamate is referred to as polyetheramine (PEA).

Example 2 Injector Hydrocarbylamine Detergents Useful in the Present Invention Injector detergents (ID) were prepared in a manner similar to that described by Honnen in Example 2 of US Pat. No. 3,438,757. In this example, a _C30 polyisobutene having a molecular weight of about 420 was reacted stepwise with chlorine and ethylenediamine to produce a polyisobuteneethylenediamine adduct.

Example 3 Carrier Fluids Useful in the Invention In the following examples, Chevron Neutral Oil 500R and Chevron Neutral Oil 600P were used as carrier fluids (CF). Chevron Neutral Oil 500R has a pour point of -12 ° C (maximum) and 40 ° C
Is a highly refined base oil with a viscosity of 98.6 cSt. Chevron Neutral Oil 600P has a pour point of 12.2 ° C (10 ° F) and a viscosity of 129.5 cSt at 37.8 ° C
Is a highly refined base oil.

Example 4 Demulsifier useful in the present invention The demulsifier (D) used in these examples to illustrate the invention was manufactured by Torad® T-32
It was a commercially available demulsifier, named Tretolite Division, Petrolite, St. Louis (MO). The demulsifier comprises a mixture of oxyalkylated alkylphenol-formaldehyde resin, polyoxyalkylene glycol and sodium arylsulfonate (1-5% by weight) in heavy aromatic naphtha (30-60% by weight). Things. Torad (registered trademark) T-
326 is the flash point (SFCC) 45.6 ° C 114 ° F), pour point (ASTM
D-97) has a reported viscosity of 263 SUS at -15 ° C (5 ° F) and 15.6 ° C (60 ° F).

Example 5 Demulsifying Test The method described in ASTM Method D-1094 was used to test the demulsifying properties. Here, the fuel phase and the interface were evaluated for light transmittance and the durability of the interface emulsion layer. The fuel additive composition was tested and evaluated numerically on a scale of 1 to 4. The number "1" was assigned the highest grade for light transmittance, and "1" was assigned the highest grade for the persistence of the interfacial emulsion layer.

The fuel additive composition of the present invention, of which Sample 6A below is a typical example, met the Grade 1 requirements in both of these tests.

Example 6 Preparation of Fuel Additive Composition A fuel additive composition was prepared. That is, 150 parts of the polyetheramine of Example 1, 25 parts of the injector cleaning agent of Example 2, 12 parts of the demulsifier, Chevron Solvent (Ch
evron Solvent) 25 (this is San
C- available from Chevron USA of Francisco
212 parts) and Chevron Neutral Oil 500R (Example 3).
450 parts were mixed with stirring in a 200 ml flask at room temperature.

Sample 6A was used as a demulsifier by Torad® T-326.
(Described in Example 4). Sample 6B contained L-1562 as a demulsifier. L-
1562 is a commercially available demulsifier purchased from Petrolite of St. Louis, MO. Sample 6C of third additive composition
Contains oleylamine as a detergent for the injector and is shown for comparison. Oleylamine is a low molecular weight, linear _C18 primary amine.

Example 7 Compatibility Test The compatibility test used was a modification of the method described in ASTM Method D-2273. However, these compositions already contain significant amounts of diluent solvent (chevron solvent).
25, a mixture of aromatic compounds for a C-9 blend), the test was performed without further dilution. The test was performed in two parts. In Part A, the sample prepared by the method of Example 6 was kept at ambient temperature, ie, room temperature (about 20-25 ° C) for 24 hours. Each sample was then visually inspected for the second phase. If a second phase was observed, the sample was centrifuged and the volume percent of the second phase was determined. If no second phase was observed, Part B of this test was performed.

In Part B, the sample was cooled to -17.8 ° C (0 ° F) and held at this temperature for 24 hours. Each sample was then visually inspected for the second phase. If a second phase was observed, the sample was centrifuged and the volume percent of the second phase was determined.

The results are shown in terms of volume percent of the second phase sediment after centrifugation, which was either a liquid, solid or a combination of both. Sediment (ie, phase 2) levels above 0.005% by volume are considered unacceptable.

The fuel additive composition of the present invention (Sample 6A) has no measurable volume percent of the second phase under these test conditions. However, significant and unacceptable levels of the second phase were observed when using L-1562 as the demulsifier (sample 6B) or using oleylamine as the injector cleaner (sample C).

For sample 6B, a liquid second phase was observed at ambient temperature. This indicates the incompatibility of the demulsifier in the fuel additive composition with other components.

Sample 6C containing oleylamine as a detergent for the injector, after cooling to -17.8 ° C (0 ° F) and centrifuging, showed a small amount (0.05% by volume) of insoluble solid precipitate. Therefore, this sample has a sediment level of 0.005% by volume.
Did not pass the criteria that they must not be exceeded.

Example 8 Intake Valve Deposition Test A fuel additive package of the present invention was added to unleaded regular gasoline such that the fuel contained the following components: 8A: 150 ppm PEA (Example 1) 25 ppm ID (Example 2) ) 450 ppm CF (Example 3, Chevron 600P) 12 ppm 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 was tested for its effectiveness in keeping the intake valves clean using a 1981 Pontiac 2.5 liter engine mounted on an engine test stand and run for 90 hours. This test simulates one type of rigorous field test characterized by light load drive conditions. The effectiveness of the additive package is determined by averaging the weight of the accumulated deposits on the intake valve obtained up to the end of the test and comparing these results with the results obtained using the same test conditions and no added fuel. Ask. A good fuel additive package capable of perfecting intake system clean retention performance typically reduces intake valve deposits of base gasoline.

Using the test conditions described above, the additive-free base gasoline produced an average of 1,090 milligrams of deposit per intake valve. The deposit of the same gasoline containing the fuel additive package of the present invention, Example 8A, using Chevron Neutral Oil 600P, averaged 23 milligrams per intake valve. Based on the above comparison, the base fuel and the added fuel containing Chevron Neutral Oil 500R (Example
8B), an average of 299 milligrams of intake valve deposits was observed. The results are summarized below. Fuel Blend: Contains no average deposit weight additive (for base fuel) 1090mg 8A 23mg 8B 299mg For both 8A and 8B, the average deposit weight is significantly less than for the base fuel and the fuel addition of the present invention 5 shows the effectiveness of the agent composition.

Example 9 Octane Demand Increase Test This test may have a gasoline additive,
It measures the likelihood of disrupting the octane requirement of a gasoline-powered engine. Over time, higher octane gasoline is required to minimize engine knock conditions due to deposit buildup in the combustion chamber. Raw gasoline has deposits that typically require a fuel with an octane number four higher than the initial fuel used to start the test to minimize the increasing engine knock conditions Give the baseline level. Gasoline additives contribute to this problem to varying degrees, and the magnitude of this contribution can be measured by comparison to engine tests using added fuels. The ORI difference observed between tests is that additional increment of the increased octane required to further minimize engine knock conditions and is commonly referred to as the octane requirement increase due to the gasoline additive package itself. You.
This value is typically referred to as "additive ORI value".

This method uses a 1975 Toyota 2.2 liter engine mounted on an engine stand and equipped with a control system to carefully adjust the test conditions and engine operating cycle. The engine is first run for 15 hours on an additive-free alkylate fuel that burns relatively cleanly. At this point, the octane requirement is measured and the fuel is exchanged for a mixture of 70% unleaded regular gasoline and 30% FCC heavy gasoline. The FCC heavy gasoline component is used during this test phase to increase the rate of deposit buildup in the combustion chamber. After 110 hours of additional engine operation, the final octane requirement is measured.

When tested in this manner, the fuel additive package of the present invention provided an octane number one-half octane higher than the octane number requirement observed for the unadded fuel (Test 9A). This increase is due to the heavy commercial polybuteneamine produced from polybutene, which has an average molecular weight of about 1450 and is stepwise reacted with chlorine and ethylenediamine, containing an average of 100 carbons per molecule, and a large amount of carrier oil. Significantly less than the increase observed for the gasoline additive package (Test 9B).

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Olsen, Ralph E. United States 94901 Dominican drive, San Rafael, California 65 (58) Fields studied (Int. Cl. ⁶ , DB name) C10L 1/22 C10M 133 / 16 C10N 40:25 WPI / L (QUESTEL) EPAT (QUESTEL)

Claims (16)

(57) [Claims] 1. A dispersant comprising: (a) a hydrocarbyl poly (oxyalkylene) amino carbamate having at least one basic nitrogen atom and having an average molecular weight of about 1000 to about 3000; (b) having at least one basic nitrogen atom, a branched-chain hydrocarbyl amine having an average molecular weight of about 300 to about 700, in which the hydrocarbyl moiety is derived from C ₂ -C ₆ olefin polymer the hydrocarbyl An injection detergent comprising an amine; (c) a fuel demulsifier which is homogenous with the other components of the final fuel additive composition; and (d) a homogeneous fuel additive comprising a natural or synthetic carrier fluid. Composition. 2. The fuel additive composition according to claim 1, wherein the hydrocarbyl groups in component (a) contain from 1 to about 30 carbon atoms. 3. The fuel additive composition according to claim 1, wherein the hydrocarbyl group in component (a) is an alkylphenyl group. 4. The fuel additive composition according to claim 3, wherein the alkyl moiety in the alkylphenyl group is tetrapropenyl. 5. The amino carbamate wherein the amine moiety is from 2 to
2. The method of claim 1, wherein the polyamine is derived from a polyamine having 12 amine nitrogen atoms and 2 to 40 carbon atoms.
Item 13. The fuel additive composition according to Item. 6. The fuel additive composition according to claim 5, wherein the polyamine is a polyalkylene polyamine having 2 to 12 amino nitrogen atoms and 2 to 24 carbon atoms. 7. The fuel additive composition according to claim 6, wherein the polyalkylene polyamine is selected from the group consisting of ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine. 8. The fuel additive composition according to claim 1, wherein the poly (oxyalkylene) moiety of component (a) is derived from C ₂ -C ₅ oxyalkylene units. 9. The composition of claim 1, wherein the hydrocarbyl poly (oxyalkylene) amino carbamate of component (a) is an alkyl phenyl poly (oxybutylene) amino carbamate, the amine portion of which is derived from ethylene diamine or diethylene triamine. 2. The fuel additive composition according to claim 1. 10. The fuel additive composition according to claim 1, wherein the branched hydrocarbyl moiety of component (b) is polypropenyl or polyisobutenyl. 11. The composition of claim 1, wherein the amine group of the branched hydrocarbylamine of component (b) is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Fuel additive composition. 12. The fuel additive composition according to claim 1, wherein the branched hydrocarbylamine of component (b) is polyisobutenylethylenediamine. 13. Component (a) is an alkyl phenyl poly (oxybutylene) amino carbamate, the amine part of which is derived from ethylene diamine or diethylene triamine, and component (b) is polyisobutenyl ethylene diamine. The fuel additive composition according to claim 1. 14. A hydrocarbon boiling in the range of gasoline or diesel, and from about 400 to about 1,200 parts per million of the following components: (a) average molecular weight having at least one basic nitrogen atom A hydrocarbyl poly (oxyalkylene) amino carbamate comprising from about 1000 to about 3000; (b) a branched hydrocarbyl amine having at least one basic nitrogen atom and having an average molecular weight of from about 300 to about 700. homogeneous with other components of (c) fuel additive composition; a and, the hydrocarbyl moiety is C ₂ -C ₆ injectors detergent comprising said hydrocarbyl amine is derived from an olefin polymer is A fuel composition comprising: a fuel demulsifier; and (d) a homogeneous fuel additive composition comprising a natural or synthetic carrier fluid. 15. A dispersant of component (a) of about 100-225 ppm,
Claim 10 wherein the composition contains about 10-70 ppm of component (b) injector cleaner, about 5-25 ppm of component (c) demulsifier and about 250-800 ppm of component (d) carrier fluid.
Item 15. The fuel composition according to Item 14, 16. An inert and stable lipophilic organic solvent boiling in the range of 65.6-204.4 ° C. (150-400 ° F.), and about 5%.
(B) a dispersant comprising a hydrocarbyl poly (oxyalkylene) amino carbamate having at least one basic nitrogen atom and having an average molecular weight of about 1000 to 3000; having at least one basic nitrogen atom, a branched-chain hydrocarbyl amine having an average molecular weight of about 300 to 700, the hydrocarbyl amines in which the hydrocarbyl moiety is derived from C ₂ -C ₆ olefin polymer A homogeneous fuel additive composition comprising: (c) a fuel demulsifier that is homogeneous with other components of the fuel additive composition; and (d) a natural or synthetic carrier fluid. A fuel concentrate comprising: