CN1064100A

CN1064100A - Fuel composition

Info

Publication number: CN1064100A
Application number: CN92100904A
Authority: CN
Inventors: E·C·莫茨甄; S·A·迪比尔斯
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1991-02-15
Filing date: 1992-02-15
Publication date: 1992-09-02
Also published as: FI924643A0; WO1992014805A1; AU1257692A; ZA921096B; HUT64100A; PL296386A1; RU2062781C1; NO923977L; DE69201538D1; FI924643A; BR9204777A; HK39596A; NO923977D0; IL100920A; MX9200591A; TW239158B; ES2072143T3; JPH05507313A; IL100920A0; ATE119192T1

Abstract

The present invention relates to automobile fuel composition.This based composition contains and is in a liquid state usually, is in fuel and following additive in the gasoline boiling range:

(A) the following amino-phenol of chemical formula:

(B) the following amine of general expression:

Each substituting group is defined in the specification.In one embodiment, component (A) and content (B) are enough to keep whole intake system cleaning.In another embodiment, component (A) and content (B) are enough to prevent or reduce the suction valve deposition generate or at this formation of deposits place it is removed.Disclosed herein as well is and keep whole intake system cleaning and prevent or reduce the suction valve deposition generating or remove sedimentary method.

Description

Fuel composition

The present invention relates to the used New-type fuel composition of oil engine and the using method of this fuel composition.

For many years, used fuel contains various additives to improve fuel performance or alleviate the problem that fuel uses and occurred when burning in oil engine in the oil engine.During the fifties and the sixties, engine design teacher generally concentrates on the exploitation high-performance enginer, seldom is concerned about the economy or the exhaust emissions problem of fuel.The fuel delivery system of the engine in this section period all is with vaporizer air-fuel mixture to be sent into combusted cylinder through pipeline.Major concern was that the freezing of vaporizer, suitable octane value, evaporator surface generate settling and fuel stability or the like at that time.In fuel, add additive,, can obtain suitable performance usually as frostproofer, plumbiferous fuel dope, washing agent and various antioxidant.The deposition at other positions is not a subject matter in the fuel delivery system, because consider mixing ratio error, this class engine generally all is designed to enriched air/fuel ratio.Higher power-part by weight means that the driver goes to note the variation and the fuel economy of peak power not too easily, and exhaust emissions neither a serious problem of paying close attention to that kind.

Up to the energy dilemma of 1970's, and the similar increase day by day to the concern consciousness of environment that occurs simultaneously, purpose is that not only the change that improves engine output just begins to be subjected to noting widely.During this period and continue up at the beginning of 1980's, the government regulations of the U.S. and whole world other countries has been formulated the restriction of increasingly stringent to exhaust emissions and fuel consumption.For reaching miniaturization and the increasingly extensive use light material that these effort that require to be done comprise various engine modifications measures, vehicle and engine.During this period, done a few thing except the control hydro carbons is discharged, the variation of fuel system is little.But human consumer at that time recognizes really that then the cleaning of fuel intake system is very important for keeping acceptable fuel consumption limit.

At the beginning of 1980's, the evaporation type oil engine begins to make way for throttling bodies formula fuel injection system.This system is at United States Patent (USP) the 4th, 487, and 002 and 4,490, No. 792, and describe to some extent in the article of Bowler (SAE Paper 800164).Fuel dope commonly used is applicable to this system usually.

At improving fuel economy, improve performance, reach the continuous requirements in aspect such as reducing exhaust emissions, automobile manufacturing company begins to adopt more advanced engine.One of trend is to use specific output height, lean-burn engine more and more.In order satisfy to increase power, improve the composite request of fuel economy and environment control etc., this class engine design becomes can be under the incendiary lean-limit or near this submaximal work, that is uses few fuel of trying one's best.Lean-burn engine requires the air-fuel ratio is controlled accurately.This does not just allow engine deposition to occur in whole fuel adjusting and inlet system.Therefore the cleaning of whole intake system has become vital top-priority problem.Further developing of fuel adjusting and inlet system, produced the engine that to work and to have premium properties effectively, and the quantity of the bad discharge that is produced is very little, and perhaps the discharge that is produced is easy to be controlled with the emission control system of catalyzer one class.One of progress of this respect is to use fuel injection system more and more widely, and for example the port fuel injection is also referred to as many ports fuel injection, and injector wherein arrives air inlet turbine or inlet mouth with the fuel spray feed.This ejector system is at United States Patent (USP) the 4th, 782, description arranged in No. 808, and its content is incorporated the part of this paper as the disclosure of invention into.The generally all very close intake valve of each injector.Injector itself is designed to have accurate tolerance, therefore is subject to the influence of dirt, the dirt that brings of fuel self for example, or owing to its position very is under the hot environment near intake valve, this just forms carbon easily on injector and the paint film shape deposits.This deposition causes having weakened the control to fuel adjusting.When the injector tip place generated deposition, injector will stop up, and perhaps is at least to have destroyed accurate fuel injection diameter.

Another problem that occurs is originally to form settling on one's body at intake valve.For the deposition that in the port fuel injected engine, generates especially severe, once one of reason of Ti Chuing be fuel injection on the hot surface of valve, thereby on valve body, form carbon laydown.

Although previous engine sometimes also easily in whole inlet system (be included in intake valve originally on one's body) form deposition, but the requirement to the engine of working under rich fuel mixture condition is so harsh, and this has just covered the disadvantageous effect to driveability.Current more advanced engine then often is difficult to allow this settling, and deposition can cause serious driveability problem, and as unsettled idle running, it is slow to start, and horsepower descends and is flame-out.

Use the decentralized additive of great amount of conventional to tend on intake valve, cause more deposition in order to overcome above-mentioned some problems, also can cause the valve adhesion.Once the someone pointed out, the decomposition of fuel dope can cause deposition and hinder valve event.

Therefore constantly study maintenance inlet system cleaning, or cleaning the method for the intake system of having polluted.

One of purpose of the present invention provides new fuel composition.

Another object of the present invention provides the New-type fuel composition that total system is kept clean.

Also have a purpose to provide the New-type fuel composition that is applicable to port burner oil engine, this composition can prevent or reduce and form deposition on intake valve.

Another purpose provides the New-type fuel composition that can satisfy one of above-mentioned purpose at least and don't can cause the valve adhesion.

Another purpose provides and makes whole inlet system keep clean method in the oil engine with gasoline as fuel.

There is a purpose to provide method again and generates deposition in the port injection-type engine on the intake valve, or it is removed in the place that has deposition to generate to prevent or to reduce.

Other purposes will mention below, and these purposes will be conspicuous after reading the application's disclosure for each is familiar with the personnel of this area utilisation technology.

Also have a purpose to provide the compositions of additives of being made up of more than a kind of additive, additive does not wherein have disadvantageous effect each other, and it can keep the inlet system cleaning and reduce or eliminate to obtain unexpected improvement aspect the intake valve deposition.

The present invention relates to automobile fuel composition, be included in the fuel that is generally liquid in the gasoline boiling range; With

(A) the following amino-phenol of chemical formula:

Each A is respectively H or the saturated substantially group based on hydrocarbon in the formula, and each T is respectively that H or carbonatoms are no more than about 28 alkyl, and respectively for being 1 integer at least, condition is the unsaturation valence mumber that a, b and c sum are no more than Ar for a, b and c; Ar can select substituent monocycle arbitrarily for use for having 0 to 3, the polycyclic aromatic composition of fused polycycle or connection, these substituting groups mainly are selected from following groups: low alkyl group, lower alkoxy, nitro, carboxyl low-grade alkyl, nitroso-group, halogen and above-mentioned two or more can be selected substituent combination arbitrarily;

(B) the following amine of general formula:

R in the formula ¹For containing about 8 alkyl, R to about 24 carbon atoms ²And R ³Be H respectively, contain 1 alkyl to about 24 carbon atoms, or the following group of general formula:

R in the formula ⁵For containing 2 alkylidene groups, R to about 8 carbon atoms ²And R ³As front definition, each R ⁴Be respectively to contain 2 alkylidene groups to about 8 carbon atoms, each X, Y and Z are respectively from 0 to about 20 integers.

In one embodiment, component (A) and amount (B) are enough to make whole inlet system to keep clean.In another embodiment, component (A) and amount (B) are enough to prevent or reduce on the intake valve form deposition or it is removed generating place of deposition.Have been found that having of another kind of interpolation component (C) liquid agent oil helps strengthen detergency power and reduce the valve adhesion.The present patent application discloses whole inlet system to be kept clean and prevent or reduce intake valve and has formed deposition or remove this sedimental method.

Embodiment preferably is described below.

(A) amino-phenol

Aromatics composition Ar

The aromatics composition Ar of chemical formula shown in I can be single aromatic nucleus, as phenyl ring, and pyridine ring, thiphene ring, 1,2,3,4-tetrahydric naphthalene ring etc., or polynuclear aromatic composition.This multinuclear composition can be a condensed; That is to say that wherein at least one aromatic proton condenses with another nuclear at 2, as at naphthalene, arrive seen in the anthracene, azanaphthalenes etc.This polynuclear aromatic composition also can be a connecting-type, and wherein at least two nuclears (or monokaryon or multinuclear) link to each other through bridged bond each other.This bridging bond can be selected from organizing key with next: carbon-to-carbon singly-bound, ehter bond, ketonic bond, sulfide linkage, the polysulfidic bond that contains 2 to 6 sulphur atoms, sulfinyl key, sulphonyl key, methene key, alkylene base key, two-(low alkyl group) methene key, low-grade alkylidene ehter bond, alkylidene group ketonic bond, low-grade alkylidene sulfide linkage, the low-grade alkylidene polysulfidic bond that contains 2 to 6 sulphur atoms, amino key, polyamino key, and the mixing key of these divalence bridged bonds.In some cases, a more than bridged bond can be arranged between the aromatic proton among the Ar.For example the fluorenes ring has two benzene nucleus to be connected with a covalent linkage through a methene key.Endorsing to regard as like this has three rings, but wherein has only two to be aromatics.The aromatic proton carbon atoms (adding any low alkyl group or the alkoxy substituent of existence) of common Ar itself.

Aromatic proton among the Ar (single, condensed, connection or both have concurrently) number can be in definite formula I integer a, work when b, the numerical value of c.For example, when Ar contained a single aromatic proton, a, b and c got 1 to 4 numerical value separately respectively.When Ar contained two aromatic protons, a, b and c can respectively be 1 to 8 integer.For trinuclear Ar composition, a, b and c can respectively be 1 to 12 integer.For example when Ar is xenyl or naphthyl, a, b and the c integer between 1 to 8 of can respectively doing for oneself.A, the value of b and c obviously is subjected to following restriction: they and total unsaturation valence link number that can not surpass Ar.

The single cyclophane perfume (or spice) that can be used as the Ar composition is endorsed with following general formula and is represented:

ar（Q）m

Wherein the ar representative contains the single ring aromatic proton (for example benzene) of 4 to 10 carbon, and each Q represents low alkyl group, lower alkoxy, nitro, nitroso-group, carboxyl low-grade alkyl or halogen atom separately, and m is between 0 to 3.Used " rudimentary " speech is meant that carbonatoms is no more than 7 group in this specification sheets and appending claims, as low alkyl group and lower alkoxy.Halogen atom comprises fluorine, chlorine, bromine and iodine atom; Usually, halogen atom is fluorine atom and chlorine atom.

Be the object lesson of single ring Ar composition below:

Deng, wherein Me is a methyl, and Et is an ethyl, and Pr is a n-propyl, and Nit is a nitro.

When Ar was multinuclear condensed ring aromatic composition, its available following general formula was represented:

Ar wherein, Q and m such as above definition, m ' between 1 to 4,

With

Represent a pair of make two the ring condensed condense key, this condense the effect make two carbon atoms become the part of each ring in adjacent two rings.The object lesson of condensed ring aromatic composition Ar has:

Deng.

When aromatics composition Ar was the polynuclear aromatic composition that connects, it can be represented with following general expression:

W wherein is the integer between 1 to about 20, ar as previously discussed, condition is the valence link that has 3 unsaturations (promptly free) in whole Ar group at least, Q and m such as top definition, each Lng represents a bridged bond, is selected from respectively with next group key: carbon-to-carbon singly-bound, ehter bond (as-O-), ketonic bond (as

), sulfide linkage (as-S-), contain the polysulfidic bond of 2 to 6 sulphur atoms (as-S _2-6-), the thionyl key (as-S(O)-), the sulphonyl key (as-S(O) ₂-), the low-grade alkylidene key is (as-CH ₂-,-CH ₂-CH ₂-,

Deng), two (low alkyl group) methene key (as CR °-), the low-grade alkylidene ehter bond is (as-CH ₂O-,-CH ₂O-CH ₂-,-CH ₂-CH ₂O-,-CH ₂CH ₂OCH ₂CH ₂-,

,-

Deng), the low-grade alkylidene sulfide linkage (as in the low-grade alkylidene ehter bond one or several-O-replaced by-S-atom), low-grade alkylidene polysulfidic bond (one or several in the low-grade alkylidene ehter bond-O-quilt-S for example _2-6-group replaces), amino key (as,

Deng, wherein alk is a low-grade alkylidene etc.), the polyamino key (as-N(alkN) _1-10, unsaturated here N valency free linkage combines with hydrogen atom or R ° of group), also can be the mixing key (each R ° is low alkyl group) of these bridged bonds.Also might in above connection aromatics composition, have one or several Ar group by condensed ring (as ar Ar

M ') replaces.

The object lesson of connecting-type aromatics composition has:

Except A ,-OH and-NT group (and any bridge linkage group) outside, do not have substituting group in all these Ar compositions usually.

Since cost, the source, reasons such as performance, the Ar composition is generally the benzene nucleus or the naphthalene nuclear of benzene nucleus, low-grade alkylidene bridging.Therefore, typical A r composition is to have the benzene of 3 to 5 unsaturation valence links or naphthalene nuclear, and therefore 1 in the above-mentioned valence link or 2 can be closed by hydroxyl is full, and remaining unsaturation valence link then becomes ortho position or contraposition as far as possible with hydroxyl.Ar preferably has the benzene nucleus of at least 3 unsaturation valence links, and one of them key is satisfied by hydroxyl and closed, and all the other 2 or 3 then become ortho position or contraposition with hydroxyl.

Group A

Amino-phenol among the present invention contains at least one group A and aromatics composition Ar Direct Bonding, and A can be respectively H or alkyl.In one embodiment, each group A is respectively H or contains the alkyl or the alkenyl of about 18 carbon atoms at most.Preferably having an A at least is alkyl.A more than alkyl can be arranged, but the alkyl on each aromatic proton is no more than 2 or 3 usually in aromatics composition Ar.It is to contain about 9 alkyl to about 750 carbon that at least one A group is preferably arranged.Alkyl A often contain at least about 30 to about 400 carbon atoms, more typical situation be at least about 50 carbon atoms to about 750 carbon atoms at most, modal is to be no more than about 300 carbon atoms.In a kind of particularly suitable embodiment, each non-hydrogen group A is an aliphatic alkyl.

When group A contains 2 during to the alkyl of about 28 carbon atoms or alkenyl, it is generally made by corresponding alkene; For example obtain butyl, obtain octyl group etc. by octene by butylene.When A is the alkyl that contains at least about 30 carbon atoms, it is aliphatic group normally, homopolymer or multipolymer (as multipolymer, terpolymer) by monoolefine that contains 2 to 10 carbon atoms or diolefine (as ethene, propylene, butene-1, iso-butylene, divinyl, isoprene, 1-hexene, 1-octene etc.) make.In general, these alkene are the 1-monoolefine, for example the homopolymer of ethene.These aliphatic alkyls also can be made by halo (as chloro or the bromo) analogue of this homopolymer or multipolymer.But the group A of alkyl form also can make from other source, as high-molecular weight monomer alkene (as 1-40 alkene) and chloro analogue and its hydrochlorinate analogue; The aliphatics petroleum fractions, the particularly analogue of paraffin and cracked thereof and chloro and its hydrogen chloro analogue, light oil, synthetic alkene is (such as the alkene that makes with the Ziegler-Natta method, and other source of knowing of this area professional polyethylene lubricating grease for example).Below before the denitrification step of Jie Shaoing, can be with method as known in the art by hydrogenation to reduce or eliminate any unsaturation valence link among the group A.

Here used " alkyl " speech is meant such group, and its carbon atom directly is connected with the rest part of molecule, and mainly presents the hydro carbons characteristic within the scope of the invention.Therefore " alkyl " speech comprises hydro carbons and is the group of hydro carbons basically." being hydro carbons basically " is meant some groups like this, be included in the group based on hydrocarbon that contains non-hydrocarbon substituent or non-carbon atom in ring or the chain, but these do not change the prevailing hydro carbons characteristic of group.

Alkyl can contain maximum three (maximum one better) non-hydrocarbon substituent or non-carbon heteroatomss in its ring or chain, have so non-hydrocarbon substituent or non-carbon heteroatoms can obviously not change the prevailing hydro carbons characteristic of group for per 10 carbon atoms.One of skill in the art understands this heteroatoms (as oxygen, sulphur and nitrogen) or substituting group (for example comprise hydroxyl, halogen is chlorine and fluorine particularly, alkoxyl group, alkyl hydrogen sulfenyl, alkyl sulfenyl etc.).

The example of alkyl comprises following three classes, but not necessarily is limited to these:

(1) hydro carbons substituting group, promptly aliphatic substituting group (as alkyl or alkenyl), alicyclic substituting group (as cycloalkyl, cycloalkenyl group); The aromatic substituent of aromatics, aliphatic series and alicyclic replacement etc.; Also comprise cyclic substituents (for example, any two above-mentioned substituting groups can form an alicyclic group) by another part Cheng Huan in the molecule;

(2) have substituent hydro carbons substituting group, that is contain the substituting group of non-hydrocarbons group, but in text of the present invention, this non-hydrocarbons group does not change " being the hydro carbons substituting group basically " these characteristics; This area professional is familiar with this class group (as halogen particularly chlorine and fluorine, hydroxyl, alkoxyl group, thiohydroxy, alkyl hydrogen sulfenyl, nitro, nitroso-group, sulphur oxygen base etc.);

(3) assorted substituting group, that is in text of the present invention the prevailing substituting group of hydro carbons characteristic, but on its ring originally formed or chain, contain non-carbon atom by carbon atom.The heteroatoms that is suitable for is conspicuous to the general professional in this area, for example comprises sulphur, oxygen, nitrogen, and some substituting groups, for example pyridyl, furyl, thienyl, imidazolyl etc. like this.In general in annular composition, for per 10 carbon atoms in the alkyl, non-hydrocarbon substituent or non-carbon atom do not surpass about 2, preferably are no more than 1.But used alkyl is pure hydro carbons usually, does not contain this non-hydrocarbons group or substituting group.

Alkyl A is preferably saturated basically.Basically saturated being meant in this group, for per 10 carbon-to-carbon singly-bounds, contained carbon-to-carbon unsaturated bond is no more than 1.Usually in this class group, for per 50 C-Cs, contained non-aromatics carbon-to-carbon unsaturated bond is no more than 1.

Alkyl A in the amino-phenol of the present invention, its character should be aliphatic basically also, that is for per 10 carbon atoms among the group A, contained carbonatoms is equal to or less than 6 non-aliphatic composition group (cycloalkyl, cycloalkenyl group or aromatic base) and is no more than 1 among the A.But for per 50 carbon atoms, contained this non-aliphatic group is no more than 1 among the group A usually, and they do not contain the non-aliphatic group of this class fully under many circumstances; That is to say that typical group A is a pure fat family.In general, the group A of these pure fat families is alkyl or alkenyl.

The example of saturated basically alkyl A concrete (but non-limiting) has: methyl; the tetrapropylene base; nonyl; triisobutyl; oleoyl; tetracontyl; the henpentacontane base; contain about 35 poly-(ethylene/propene) based mixtures to about 70 carbon atoms; contain about 35 to the oxygenolysis of about 70 carbon atoms or poly-(ethylene/propene) based mixtures of machinery decomposition; contain about 80 poly-(propylene/1-hexene) based mixtures, contain the polyisobutene based mixtures of 20 to 32 carbon atoms, on average contain the polyisobutene based mixtures of 50 to 75 carbon atoms to about 150 carbon atoms.The raw material preferably of alkyl A is a polybutene, and it is by C ₄Petroleum streams (the butylene weight content is 35% to 75%, and the iso-butylene weight content is 15% to 60%) polymerization in the presence of Lewis an acidic catalyst (as aluminum chloride or boron trifluoride) obtain.The isobutylene repeat units (in all repeating units, accounting for more than 8.0%) that mainly contains following configuration in this polybutene:

Connecting alkyl A on the aromatics composition Ar of amino-phenol of the present invention can realize with many methods that this area professional knows.A kind of method of particularly suitable is Friedel-Crafts reaction, a kind of alkene in this reaction polymkeric substance of ethylene linkage (as contain) or its halo or hydrohalogenation analogue in the presence of the Lewis an acidic catalyst with phenol reactant.Realize that the method and the condition of this reaction know for this area professional.It for example is the discussion of " alkylation of phenol " literary composition referring to title, this article publication is gone up (this encyclopedia is published by the subordinate's of New York John Wiley company Intersc-ience publishing company) at " chemical encyclopedia " the 3rd edition the 2nd the 65th to 66 page of rolling up that Kirk-Othmer compiles, also can be referring to United States Patent (USP) the 4th, 379,065,4,663,063, with 4,708, No. 809, all these articles are all incorporated the part of the application's conduct about the disclosure of aromatic alkylation into clearly at this.For the professional of this area, be easy to expect some other same being suitable for and easily method can be used to that the radicals R based on hydro carbons is connected to aromatics composition Ar and get on.

Investigation formula I can see that the used amino-phenol of the present invention contains a group in the following various substituting group at least: hydroxyl, group A, and amino group as defined above ,-NT ₂Each above-mentioned group must be connected with the carbon atom as the part of aromatic proton in the Ar composition.But and do not require that each this substituting group all is connected to (if a more than aromatic nucleus is arranged) on the same aromatic nucleus in the Ar composition.

Amino group-NT ₂

Amino-phenol among the present invention contains the substituting group of one-NT form at least.Each T is respectively H or contains the alkyl that is no more than about 28 carbon atoms.In one embodiment, each T is respectively H or alkyl or alkenyl.Alkyl or alkenyl contain 1 to about 28 carbon atoms, and most cases is to about 18 carbon atoms from 1.In a kind of embodiment preferably, having a T at least is H, and another T is H or alkyl or alkenyl.In a kind of better implement scheme, two T are H.

Subscript c represents can be as substituent number of amino groups on the Ar group.Have so amino substituting group at least, also can have severally, this depends on the value of subscript a and b.The numerical value of c is better between 1 to about 5.C etc. 1 in embodiment preferably.

Subscript b represent aromatics composition Ar go up as substituting group occur-number of OH group.Subscript b must equal 1 at least; But as top defined, b also can be the numeral greater than 1.Can on aromatics composition Ar, occur-maximum number of OH group depends on the value of subscript a and b.On the Ar as substituent-OH group with 1 to 5 about better, in suitable especially embodiment, on Ar, have only an OH substituting group, that is subscript b equals 1.

In embodiment preferably, amino-phenol of the present invention contain above-mentioned substituting group-OH and-NT ₂Each one (being that b and c are 1) has an A group to be the group based on aliphatic hydrocrbon, and remaining A group is H, has only a single aromatic nucleus, preferably benzene.A Shi Yi class amino-phenol can be represented by the formula especially:

R ' group is saturated substantially alkyl in the formula, contains to have an appointment 30 to about 400 aliphatic carbon atoms, and R ' becomes ortho position or contraposition, R, and " be low alkyl group, hydroxyl low-grade alkyl, lower alkoxy, nitro or halogen, p is 0 or 1 with hydroxyl.General p gets 0, and R ' is saturated substantially pure hydro carbons aliphatic group.It becomes the alkyl or the alkenyl of contraposition with-OH substituting group often.Generally have only an amino, in suitable amino-phenol-NH ₂Also can there be two.

In a kind of better implement scheme of the present invention, the general expression of used amino-phenol is:

R ' is obtained by the homopolymerization of 1-alkene or the multipolymer that contain 2 to 10 carbon atoms in the formula, on average contains about 30 to about 400 aliphatic carbon atoms, R " defines with p such as front.Usually, R ' is made by polymeric ethene, propylene, butylene and their mixture.It generally makes with polybutene.R ' often contains at least about 50 aliphatic carbon atoms, and p equals 0.

Amino-phenol among the present invention can make with many different synthetic routes.These synthetic routes are different aspect the order of the pattern of used reaction and used reaction.For example, the available alkylating reagent of aromatic hydrocarbons (as benzene) (for example polyolefine) alkylation is to generate alkylating aromatics intermediate.This intermediate for example, can be nitrated again to generate poly-nitro intermediate.Poly-nitro intermediate can be reduced to diamines again, and it carries out diazotization again and makes an amino be converted into hydroxyl with the water reaction, thereby obtains required amino-phenol.Another kind of way is, by being converted into hydroxyl to generate hydroxyl 4-nitro alkyl aromatic compound with the caustic alkali congruent melting, the latter is reduced into required amino-phenol again with a nitro of poly-nitro intermediate.

The suitable route of the amino-phenol that another kind of preparation the present invention is used is to make alkylation of phenol to generate alkylated phenol with a kind of olefin alkylation reagent.This alkylated phenol can carry out nitrated again and generate the intermediate nitrophenols, at least a portion nitroreduction of the latter is become amino just can be translated into required amino-phenol.

The very familiar the whole bag of tricks that makes alkylation of phenol of one of skill in the art, the article of the publication of mentioning in the above on " chemical encyclopedia " that Kirk-Othmer compiles also has report.It also is known making the nitrated method of phenol.For example referring to Kirk-Othmer " chemical encyclopedia " the 2nd edition the 13rd volume, title of article be " nitrophenols ", step on the 888th page and subsequent some pages or leaves, also has some monographs as " aromatics replacement; Nitrated and halogenation ", the author is P.B.D DeLaMare and J.H.Ridd, is published in nineteen fifty-nine by New York Academic press; " nitrated and aromatics reactive behavior ", the author is J.G.Hogget, goes out out the moon in 1961 by the Cambridge University Press, London; ; Nitro and nitroso-group chemistry " " " editor is Henry Feuer, published in 1969 by New York Interscience publishing company, also has United States Patent (USP) the 4th, 347,148; 4,320,020 and 4,379, No. 065, the content of all these articles is incorporated the part of the application as this paper disclosure relevant with the method for preparing nitroaromatic and these compounds itself into.

Aromatic hydroxy compound can be used nitric acid, the mixture of nitric acid and other acid (as sulfuric acid or boron trifluoride), and nitrogen tetraoxide, nitronium tetrafluoroborate and acyl group nitrate etc. carries out nitration reaction.In general, concentration such as nitric acid between about 30% to 90% is exactly the agent of a kind of nitration reaction easily.Basically be the inert liquid diluent with solvent (as acetate or butyric acid) thus can improve reagent contacts and helps the carrying out that react.

Nitrated condition of hydroxyaromatic compounds and concentration are known in the art.For example, reaction can approximately-15 ℃ to about 150 ℃ temperature, carry out, generally between about 25 ℃ to 75 ℃, the reaction times should be enough to the degree of nitration that reaches required.

Generally speaking, treat that the per 1 mole aromatic proton in the nitrated hydroxyl aromatic intermediate needs about 0.5 to 4 mole nitrating agent, occurrence depends on specific nitrating agent.If a more than aromatic proton is arranged, then can increase the consumption of nitrating agent in proportion according to the number of this nuclear existence in the Ar composition.If help forward reaction or reaction is quickened, then can use excessive about 5 moles nitrating agent (with regard to each single ring aromatic proton) at most.

With reducing aromatic nitro compound is that corresponding amine is also known.For example referring to Kirk-Othmer " chemical encyclopedia " the 3rd edition, the 3rd volume, the article on the 335th page to 376 pages, its title be " reduction prepares amine ".In general, this reduction reaction such as can (if necessary or favourable) palladium for example, platinum and oxide compound thereof, nickel arranged in the presence of the metal catalyst, chromium-coppers (copperchromite) etc. carry out with hydrogen, carbon monoxide or hydrazine (or its mixture).In this catalytic reduction reaction, also can use promotor, as the oxyhydroxide or the amine (comprising amino-phenol) of basic metal or alkaline-earth metal.

Having in the presence of the acids (example hydrochloric acid), also can carry out reduction reaction with reducing metal.Representational reducing metal has zinc, iron and tin, or its esters.

Nitro also can be reduced in the Zinin reaction, and this is at New York John Wiley ﹠amp; Sons publishing company is discussed since some pages or leaves of the 455th page in " organic reaction " the 20th volume of publishing in 1973 to some extent.In general, the Zinin reaction is compound (as alkali metalsulphide, polysulfide and sulfhydrate) the reduction nitro with negative divalent sulfur.

Nitro can reduce by electrolytic action, for example referring to the top exhausted article that draws: " reduction preparation amine ".

A kind of method for making preferably of the used amino-phenol of the present invention is that the hydrogen reduction nitrophenols is used in the metal catalyst existence of discussing in the above down.This reduction reaction generally is to carry out under about 15 ℃ to 250 ℃ temperature, and hydrogen pressure is about 0 to 2000 pound/square inch (gauge pressure).Reaction times generally changed between about 0.5 to 50 hour.Obtain the amino-phenol product with the method for knowing (, filtering extraction etc. as distillation).

The another kind of the used amino-phenol of the present invention method for making preferably is with at least a hydrazine reaction thing reduction oil of mirbane that contains, also can be chosen in arbitrarily at least a metallic-agent of Lu paper Xun furan furan carries out under existing.

Used hydrazine source is hydrazine, hydrazine compound among the present invention, or the hydrazine that can produce sufficient amount with the mixture of the hydrazine compound of nitrophenols reaction.Hydrazine, hydrazine compound and many hydrazines source are known to this area professional.The book of by name " hydrazine " shown referring to Charles C.Clark for example, this book is published in nineteen fifty-three by the Mathieson chemical company of Baltimore, the Maryland State, particularly referring to wherein 31 to 71 pages and 120 to 124 pages; Also having a title is " hydrazine chemistry ", and the author is L.F.Audrieth and B.A.Ogg, and this book is published in nineteen fifty-one by New York Joho Wiley and Sons publishing company, particularly wherein 209 to 223 pages.

For the consideration of economy and easy handling, the solution of hydrazine, particularly hydrazine and water and other solvents/diluents is preferably.

In embodiment preferably, nitrophenols and the reaction that contains the hydrazine material are carried out in the presence of the metallic hydrazine decomposing catalyst not having.This means what reaction was to carry out in not containing the reaction mass that q.s containing metal catalyzer exists, contain therefore that the speed of the decomposition of hydrazine material or reaction or course are not subjected to obviously to influence or unaffected basically.Metal also might exist with pure metal, alloy or the chemical combination form parts as reactor metal equipment, for example agitator, pipeline, container, probe etc., though the metal of this form contacts with reaction mass, can obviously not influence the decomposition that contains the hydrazine material in the material or the course or the speed of reaction.In this case, with regard to purpose of the present invention, can think that reaction carries out in the presence of the containing metal hydrazine decomposing catalyst not having.

Reduction reaction proceeds in the nitro intermediate mixture at least about there being 50%(generally to be about 80%) nitro be converted into till the amino.The typical production of the used amino-phenol of the present invention described above can be summarized as follows:

(I) carries out nitrated with at least a nitrating agent at least a compound with following chemical formula, contain first reaction mixture of nitro intermediate with generation:

A is H or saturated substantially alkyl in the formula, and c equals 1 integer at least, and condition is the unsaturation valence mumber that a and c sum are no more than Ar '; Ar ' is the aromatics composition, can have 0 to 3 be selected from below the substituting group of one group of group: low alkyl group, lower alkoxy, carboxyl low-grade alkyl, nitro, halogen, or the two or more substituent combinations that can select for use arbitrarily, its condition is that (a) Ar ' has a hydrogen atom and carbon atom Direct Bonding as aromatic proton part at least, (B) when Ar ' be the phenyl ring that has only a hydroxyl, and when having only a group A to be alkyl, this hydrocarbyl group A becomes ortho position or contraposition with described hydroxyl substituent;

(II) is reduced into amino with the nitryl group at least about 50% in above-mentioned first reaction mixture.

Usually this just mean in following compound of chemical formula or compound will about at least 50% nitroreduction for amino:

Each A in the formula is respectively H or alkyl, and it is 1 integer at least that a, b and c are respectively separately, and condition is a, and b and c sum are no more than the unsaturation valence mumber of Ar; Ar has 0 to 3 substituent aromatics composition, and substituting group can be selected from following one group of group: low alkyl group, and lower alkoxy, carboxyl low-grade alkyl, nitro, halogen, or 2 or a plurality ofly above-mentionedly can select substituent combination arbitrarily for use; Its condition is, when Ar is the phenyl ring that has only a hydroxyl, and when having only an A to be alkyl, this hydrocarbyl group A becomes ortho position or contraposition with described hydroxyl substituent.

Reduce nitrated phenol (nitrophenols) method and by and the product that obtains at United States Patent (USP) the 4th, 320,020; 4,425,138 and 4,724, in No. 1,096,887, No. 091 and the Canadian Patent introduction is arranged.All these contents are specially incorporated the part of the application as the disclosure relevant with amino-phenol at this.

The following examples are used for specifying several amino-phenols that can be used in the composition of the present invention.Concerning the professional of this area, use other amino-phenol and be conspicuous with the amino-phenol of other method preparation.These embodiment will limit the scope of the invention.Unless do clear and definite explanation in addition, all umbers and per-cent all refer to weight, and temperature is degree centigrade.

Embodiment 1

Make phenol and number-average molecular weight be about 1000(in the presence of boron trifluoride/phenol catalyzer to press assay method to measure having with vapor infiltration) the polybutene reaction and the preparation alkylated phenol.Remove with after-filtration in the catalyzer warp.Product filtrate is stripped to 230 °/760 mmhg (vapour temperature) earlier, further is stripped to 205 °/50 mmhg (vapour temperature) again, and the residue that obtains is the alkylated phenol of purifying.

The mixture that 18.4 parts of concentrated nitric acids (69% to 70%) and 35 parts of water are formed slowly joins the alkylphenol by 265 parts of purifying, and the boiling point that 176 parts of mixed mineral oil and 42 parts of petroleum naphthas are formed is about in 20 ℃ the mixture.Reaction mixture stirred 3 hours down at about 30 to 45 ℃, was stripped to 120 °/20 mmhg (vapour temperature), obtained the oil solution of required nitrophenols intermediate after the filtration.

With 1500 parts of above-mentioned intermediates, 642 parts of Virahols and 7.5 parts of carrier bands are in the mixture that the nickel on the Kieselguhr catalyzer is formed is packed autoclave under nitrogen atmosphere.With nitrogen purging and find time autoclave to be boosted to 100 pounds/square inch (gauge pressures) with hydrogen after three times, and begin to stir.Reaction mixture remains in 96 ℃ and down amounts to 14.5 hours, common goes into 1.66 mol of hydrogen therebetween.Behind nitrogen purging three times, reaction mixture filters, and filtrate is stripped to 120 °/18 mmhg.The required amino-phenol product that filtration obtains is an oil solution.

Embodiment 2

The mineral oil solution (containing 43% mineral oil) of the nitrated phenol of alkylation described in 1900 parts of embodiment 1 is heated to 145 ℃ in nitrogen atmosphere.Added the hydrate of 70 parts of hydrazines then within 5 hours lentamente in mixture, mixture temperature should remain in about 145 ℃ therebetween.Mixture postheating to 160 ℃ 1 hour is collected 56 parts of water overhead products therebetween.The hydrate that adds 7 parts of hydrazines again kept mixture again 1 hour under 140 ℃.130 ℃ are filtered the oil solution that obtains required product, wherein nitrogenous 0.5% down.

Listed other amino-phenol that can be used as composition A in the present composition in the Table A.

Table A

Implement hydroxyaromatic compounds title nitric acid ⁽¹⁾Method of reducing

The example mole number

3 tetrapropylene base fortified phenols, 1 H ₂-C catalyst+Pd

4 the same N ₂H ₄.H ₂O

5 with embodiment 12 N ₂H ₄.H ₂O

6 with embodiment 12 H ₂-Kieselguhv

Catalyzer+Ni

70 (propenyl) fortified phenol, 1 H ₂-C catalyst+Pd

8 polybutene (about 100 carbon 1 H ₂-PtO ₂

Polybutene) fortified phenol

9 C ₂₅Alkylphenol 2 NH ₃/ H ₂S

10 2,2 '-dimerization (isobutyl 2.2 H ₂-Kieselguhr

Alkene) base-4,4 '-two catalyzer+Ni

Xenol (molecular weight

2500）

11 4-four (propylene) base-2 1 NH ₃/ H ₂S

-hydroxyl anthracene

12 4-octadecyls-1,3,2 H ₂-Kieselguhr

-dihydroxy-benzene catalyzer+Ni

13 2-gather (propene/but-1-ene-1 NH ₃/ H ₂S

1) base-4,4 '-different

Propylidene-bis-phenol ⁽²⁾

14 the same 1 H ₂-C catalyst+Pd

Annotate the nitric acid mole number of (1) every mole of " single ring " aromatic proton;

The mol ratio of annotating (2) propene/but-1-ene-1 is 2: 3.

(B) amine

The amine that can be used as composition in the fuel composition of the present invention (B) is the defined amine of general formula (I) of front.They comprise monoamine and polyamines, can be basically based on amine, azanol, the ether amine of hydro carbons with contain amine and other amine of one or more alkoxyl groups.

In embodiment preferably, the x of formula I, y and z equal zero respectively.Such amine is the amine of hydro carbons basically just, comprises the hydro carbons primary amine, R wherein ¹For containing 8 to about 24 carbon atom alkyls or alkenyl, from about 14 better to about 18 carbon atoms, R ²And R ³Be H.

The representative example of kiber alkyl amine is the primary amine (product that Yi Linuo provides according to the Armak chemical company in Chicago, state) of aliphatic fat primary amine and commercial being called " Armeen ".Typical aliphatic amide comprises alkyl amine, as the N-hexylamine, and N-octylame, N-decyl amine, N-lauryl amine, N-tetradecylamine, N-pentadecyl amine, N-hexadecylamine, N-octadecylamine (stearylamine) or the like.These Armeen primary amine commodity have distillation level and two kinds of grades of technical grade.This amine also can be buied from Sherex chemical company, and commodity are called " Adogen ".

The thiazolinyl primary amine contains the alkene unsaturated link(age) in its alkyl.Therefore the R group contains 1 or the unsaturated position of several alkene according to chain length, and per 10 carbon atoms are no more than 1 two key usually.Its representational amine has dodecylene amine, 9-tetradecene amine (myristoleyamine), 9-cetene amine, oleyl amine and inferior oleyl amine (linoleylamine).This class unsaturated amine also can be buied, commodity Armeen by name or Adogen.

The same mixing-in fat primary amine in addition that is suitable for is as soybean amine, coconut amine, tallow amine, C _20-22Amine or the like.These amines can be buied equally, commodity Armeen by name and Adogen, for example, and Armeen S, Armeen T, Adogen 101, Adogen 160 etc.

Another kind of useful alkyl primary amine is an alkyl amine.The carbon atom that nitrogen wherein direct and on the amino links to each other is a tertiary carbon atom.Each substituting group on this carbon atom is alkyl, and is better with alkyl or alkenyl.It is to contain 5 alkyl to about 25 carbon atoms that a substituting group is preferably arranged, and two other substituting group then is a low alkyl group, promptly contains 1 to about 7 carbon atoms, and it is better to contain 1 to 3 left and right sides carbon.In embodiment preferably, it is to contain about 5 alkyl to about 19 carbon that a substituting group is arranged, and two other substituting group is a methyl.This primary t-alkyl-amine comprises tert-Octylamine and C _12-14And C _18-22Amine mixture of isomers in the scope, they can be buied, and commodity are called " Primene " (Rohm of philadelphia, pa; The supply of material of Hass company).

This alkyl amine also comprises secondary amine (R wherein ²Or R ³One of be not H) and tertiary amine (R wherein ²And R ³Not H).

Secondary amine comprises dialkylamine, for example, and its R ¹For containing 8 alkyl to about 24 carbon atoms, preferably from about 14 to about 18 carbon atoms, with alkyl or alkenyl for well; R ²And R ³One of for containing 1 alkyl to about 24 carbon atoms.In one embodiment, R ¹And R ²Or R ³In one of be respectively and contain 8 alkyl or alkenyls to about 18 carbon atoms.In another embodiment, R ¹For containing about 8 alkyl or alkenyls to about 18 carbon, and R ²Or R ³First for containing 1 alkyl or alkenyl, for example methyl, butyl, propyl group, sec.-propyl, octyl group etc. to about 9 carbon atoms.

Alkyl secondary amine also comprises R ²Or R ³One of be the amine of group shown in the formula III, Y in the formula and Z are zero, R ⁵, R ²And R ³Define as the front.Comprise aliphatic diamine in these amine, fat polyamine two amines (comprising monoalkyl or dialkyl group) for example, symmetrical or asymmetrical quadrol, propylene diamine (1,2 or 1,3), and above-mentioned polyamine analogs.The commodity fattiness amine that is suitable for has " Duomeen C " (N-coconut palm base-1, the 3-diaminopropanes), " Duomeen S " (N-beans base-1, the 3-diaminopropanes), " Duomeen T " (N-tallow base-1, or " Duomeen O " (N-oleyl-1,3-diaminopropanes) the 3-diaminopropanes).The diamines that " Duomeens " sells for the merchant, they have introduction in the product information catalogue 7-10R1 of Yi Linuo according to the Armak chemical company in Chicago, state.

The amine based on hydrocarbon that is suitable for also comprises tertiary amine.This amine is meant its R ¹And R ²And R ³All be the alkyl of above definition, and X, Y and Z are zero amine.R ¹Better for alkyl or alkenyl, that especially good is R ¹Carbon atom quantity from about 14 to about 18.In one embodiment, R ²And R ³All be to contain about 8 aliphatic groups to about 24 carbon, it is better to be no more than about 18 carbon.Representational tertiary amine has three (C _8-10) amine, three-hydrogenated tallow amine, two-octadecyl methylamine, three-tridecyl amine etc.All these amine all can be buied by trade(brand)name Adogen.

The hydro carbons tertiary amine that is suitable for also comprises its R ²With R ³All non-H, and one of them is a group shown in the formula III at least, and wherein Y and Z are zero amines.Therefore having an amine group at least is tertiary amine groups, also has other amido, and they are primary, the second month in a season or tertiary amine, depend on various substituent definition in the formula III.

Ether amine also can be used in the fuel composition of the present invention.Ether amine is exactly the amine that the X in the formula I equals 1.Ether amine can be primary, the second month in a season or tertiary amine, can be oxyalkylated amine, that is to say, Y and Z can be greater than zero, and R ²And R ³Can not H.But ether amine is better with primary amine, secondary amine or diamines.The example of ether amine has R wherein ¹The amine that contains 8 to 24 carbon, better with 8 to 15 carbon, R ⁴For containing about 2 thiazolinyls, better to about 8 carbon with 3 to about 8 carbon.R preferably ¹Contain about 12 to about 15 carbon atoms, R ⁴Contain 3 carbon atoms.

Ether amine has the merchant to sell, for example commodity Adogen(Sherex chemical company by name) or Atlanta, Surfam(Georgia State Mars chemical company).Object lesson has: Adogen 183(C ₁₃Ether amine), Adogen 184(C ₁₄Ether amine), the branched C of Surfam P14AB( ₁₄Ether amine), more than being the propylamine class, is exactly Adogen 583(N-(13 ether propyl group in addition) propylene diamine), it belongs to the propylene diamine class.

In another embodiment, Y and Z have at least one to be not equal to zero, and X can be zero or at most to about 20, with zero better.According to R ²And R ³Value, these amines can be secondary amine or tertiary amine.R ¹For well, it is better to contain at least 12 carbon with alkyl or alkenyl for group, contains 14 better to about 18 carbon atoms, and X is zero.

When one of among Y or the Z being zero, this amine is exactly the amine of monoalkoxyization.In general, the general formula of this amine is:

R in the formula ¹And R ⁴Define as the front, n is 1 to maximum about 20 integer, and Y is an alkyl, and is better with alkyl or alkenyl, and carbon atoms 1 is to about 24, with 8 better to about 18 carbon atoms, and Z and the R that provides previously ²Or R ³Implication identical.Representational example comprises two-oleyl thanomin, N-methyl, N-octyl group Propanolamine etc.

Y and Z are greater than zero integer better.These amine can be monoamine or polyamines.These amine can or contain the diamines of a primary amine and a secondary amine group and epoxide (as oxyethane or propylene oxide) reaction and making with primary amine.

These amine are preferably ethoxylation or propenoxylated aliphatic amide, that is R ⁴Be ethyl or propyl group.

In one embodiment, X equals zero, and Y and Z are from 1 to about 20 integer, R ²And R ³Respectively be H or alkyl, alkyl or alkenyl are better.R in most cases ²And R ³Be H, Y and Z are from 1 to about 10 integer, and especially about from 1 to 5 better.In most cases Y and Z get 1.R ¹Be preferably and contain 8 alkyl or alkenyls to about 18 carbon, it is better to contain 12 carbon at least, often from 14 to about 18 carbon atoms at most.

The example of this amine has the aliphatic amide of alkoxylate (being preferably ethoxylation or propoxylation), for example oxyalkylated octylame, lauryl amine, 15 carbon alkenyl amines, oleyl amine, tallow amine etc.

In another embodiment, R ²And R ³In have at least one to be the group shown in the formula III, R wherein ⁵For containing 2 alkylidene groups to about 8 carbon atoms, better with 2 or 3 carbon atoms, Y and Z are integer as defined above, preferably equal zero R ²And R ³As front definition, preferably H.

The example of this class amine comprises the aliphatic diamine of alkoxylate (being preferably ethoxylation or propoxylation), as N-oleyl propylene diamine, and N ', N '-dihydroxy ethyl propylene diamine, and the derivative of soya-based, coco group, tallow base, octadecyl.

The amine of particularly suitable is " Ethomeens " and " Ethoduomeens ", and this is the serial commodity mixture of the ethoxylated fatty amine that provides of Armak company." Ethomeens " amine that is suitable for comprises " Ethomeen C/12 ", " Ethomeen S/12 ", " Ethomeen T/12 ", " Ethomeen O/12 " and " Ethomeen 18/12 ".At " Ethomeen C/12 ", in " S/12 " and " T/12 ", R ¹Be the mixture of alkyl and alkenyl, obtain by Oleum Cocois, soya-bean oil and tallow respectively, in " Ethomeen O/12 " and " 18/12 ", R ¹Be respectively oleyl and octadecyl.In corresponding " Ethoduo-meens " amine, R ¹Defined the same with the Ethomeens that introduces above.

(C) liquid agent oil

Liquid agent oil can be used in the fuel composition of the present invention.Available liquid agent oil can be natural oils or synthetic oils, or their mixture.Natural oils comprises mineral oil, vegetables oil, animal oil and the oil that obtains from coal or shale.Synthetic oils comprises hydrocarbon-type oil (as alkylating aromatic oil), olefin oligomer, ester class (ester that comprises poly carboxylic acid and polyvalent alcohol) etc.From cost and the consideration of being easy to get property, better with mineral oil.

Containing unsaturated composition, to be no more than about 20% paraffin oil especially suitable, also is that ethylene linkage is no more than 20% in the C-C.

The kinematic viscosity range of liquid agent oil under 100 ℃ is preferably about 10 to about 20 centistokes, from about 11 better to about 16 centistokes, preferably from about 11 to about 14 centistokes.If the liquid agent oil viscosity is too high, the problem that may occur is to cause boosting of octane rating demand growth trend (ORI), and at this moment engine can improve with the working hour the demand of octane value.

Have been found that amino-phenol and the amine of the interior liquid agent oil that uses of scope in the present invention of defined can improve decontamination dirt performance and reduce the tendency that valve is adhered here.The quantity of various additives is included in individual event quantity used in the fuel composition, provides below with the relative consumption of additive.

Fuel

The fuel that the present invention relates to is in a liquid state in the gasoline boiling range usually.Such fuel is known this area professional, and done qualification in the D-439 standard of ASTM (American society for testing materials) (ASTM), this standard is incorporated this paper into as the part of this paper to the disclosure of the detailed description of fuel that is applicable to the present composition clearly at this.Can be used for the fuel in the present composition, the general main fuel that is in a liquid state usually that contains is as the hydrocarbon petroleum distillate fuel.The fuel that can be used in the present composition also can contain the non-hydrocarbons material, as alcohols, ethers, organic-(as methyl alcohol, ethanol, diethyl ether, methyl ethyl ether, Nitromethane 99Min.s) such as nitro-compounds.These fuel can be made by plant or raw mineral materials, for example comprise petroleum crude oil, coal, cereal, shale and other source.The example of suitable fuel mixture has gasoline to add ethanol, gasoline adds Nitromethane 99Min. etc.Fuel is gasoline, thickened oil and gasoline-thickened oil mixture preferably, and these fuel all meet in the above-mentioned ASTM D-439 standard definition to automobile gasoline.With gasoline is best.

Fuel composition of the present invention can contain other additive that this area professional knows.Can comprise octane promoter (as the lead tetraalkyl compound) in them, deleading agent (as haloalkane), pigment, antioxidant (as hindered phenol), rust-preventive agent (as alkylating succsinic acid, succinyl oxide and derivative thereof), fungistat, gum deposit inhibitor, metal passivator, demulsifying agent, frostproofer etc.Fuel composition of the present invention can be leaded or lead-free fuel.Better with lead-free fuel.

The front was once mentioned, and In one embodiment of the present invention, automobile fuel composition contains the cleaning that certain quantity of additive is enough to keep whole inlet system.In another embodiment, the consumption of additive is enough to prevent or reduces on the intake valve that deposition generates or removed in that sedimentary place takes place.The relative weight ratio of amino-phenol (A) and amine (B) is preferably from about 150: 1 to about 1: 100.In fuel, amino-phenol content be per 1000 barrels of fuel about 10 to about 150 pound weight, amine content be per 1000 barrels of fuel about 1 pound to about 100 pound weight.This fuel can also contain liquid agent oil (C).(A) and relative quantity (C) (weight ratio) preferably from about 1: 20 to about 3: 1.Can contain 30 pounds of the liquid agent oil (is benchmark with per 1000 barrels of fuel) of having an appointment in the fuel composition to about 150 pound weight.

Although all be when representing additive amount among the present invention,, PTB numerical value is converted into ppm(ppm of calculating by weight) thereby can multiply by 4 with how many pounds (PTB) of per 1000 barrels of fuel.

Several fuel compositions that following example explanation the present invention relates to.Except as otherwise noted, all umbers are parts by weight, and the quantity of amino-phenol and other additive is all by there not being the mineral oil thinner to represent basically.Dummy suffix notation PTB represents the poundage of additive in per 1000 barrels of fuel.

Table 1 is listed several unleaded gas fuel compositions that the present invention relates to, and the additive capacity that provides is the poundage in per 1000 barrels of gasoline.

Introduce a kind of multifunctional additive for lubricating oils that is used for fuel below.All umbers are parts by weight.

Enriched material

The composition weight umber

Varsol 9.32

Oleyl amine 3.71

The amino-phenol 34.59 of embodiment 2

Liquid agent oil 51.88

C ₁₆Succinyl oxide/the alkanolamine 0.31 that replaces

Reaction product

Metal passivator 0.19 based on salicylidene

With the about 6400ppm of 1600PTB() above-mentioned enriched material prepare fuel composition.This processing is to carry out disposable cleaning to the fuel delivery system that dirt is arranged that comprises port fuel injector and intake valve.

Therefore, can clean with a kind of Fuel Petroleum for a fuel delivery system that dirt is arranged that comprises port fuel injector and intake valve, containing in this fuel has an appointment 200 to about 1000PTB(is preferably about 700PTB) amino-phenol (A) and about 20 to about 100PTB(be preferably about 70PTB) amine (B).

The amine detergent additive that polymer-based group commonly used replaces is very effective aspect control vaporizer deposition, handles consumption then also is effective to the deposition that reduces on the fuel injector if improve it.But the raising additive amount can increase the deposition on the intake valve.Think that in the past dispersion agent and liquid agent use the deposition that can control delivery system together.Beat all is that fuel composition of the present invention can make whole inlet system cleaning simultaneously, and reduces or eliminates the deposition of intake valve.

Another problem that the amine dispersion agent that uses polymer-based group to replace is brought is between the amine dispersion agent that replaces of polymerization alkyl and the various aliphatic amide (for example being determined those amines as component of the present invention (B)) disadvantageous interaction to be arranged.Use the fuel dope processing fuel of this routine that the intake valve deposition is increased.

If the amino-phenol among the present invention (A) is used from the gasoline with amine component (B), does not then not only cause the significant adverse effect of the clean mis-behave of inlet system, and also having synergistic effect aspect the minimizing intake valve deposition.

The beyond thought advantage of following data acknowledgement fuel composition of the present invention.With BMW company intake valve deposition test method fuel is evaluated.

The fuel appraisal procedure is to carry out on BMW318i type car travels 10,000 miles basis.This car is equipped with 1.8 liters of four cylinder engines and automatic transmission system.Test begins with the new intake valve of carefully weighing.Use 10,000 miles of candidate's operating fuels, take cylinder head then apart, again the weighing intake valve.

Raw data comprises intake valve deposition rated value and weight, the photo of intake valve.But significant data is the actual deposition weight on the intake valve after 10,000 miles of travelling.One of be included into fuel in three classes by following standard test back, and these standards are to set by the mean value of four intake valves:

1) the highest 100 milligrams: as to satisfy the intake valve neatness standard that BMW-NA does not restrict driving and sails mileage.

2) the highest 250 milligrams: as to satisfy BMW-NA and travel 50,000 miles with interior intake valve neatness standard.

3) above 250 milligrams: do not satisfy BMW-NA intake valve neatness standard.

Preparation Fuel Petroleum composition wherein contains amino ethyl ethanolamine that the polybutene of 44PTB replaces and the liquid agent oil (being made up of the residual oil bright stock) of 82.5PTB.The valve that the BMW test obtains is deposited as 19.2 milligrams to 171.5 milligrams, average 94.5 milligrams.

Preparation and above similar several Fuel Petroleum compositions, but contain a kind of amine of meeting of some amount in every kind of composition to the described requirement of component (B).The mean value that the BMW test of these fuel obtains is about 215 milligrams of depositions.

Prepare two kinds of Fuel Petroleum compositions, contain 75PTB(and be calculated as 45PTB by no oil) the liquid agent oil of forming by the residual oil bright stock as this paper embodiment 1 described amino-phenol and 112.5PTB.The valve deposition value that the BMW test obtains is 35.3 to 100.6 milligrams, average 67 milligrams.

Prepare three kinds of Fuel Petroleum compositions, contain 80PTB(and be calculated as 48PTB by no oil) embodiment 1 in amino-phenol, the liquid agent oil of being made up of bright stock of 120PTB, every kind of composition also contains a certain amount of a kind of amine that meets the described requirement of component (B).About 45 milligrams of the valve deposition average out to that this fuel BMW test obtains.

Though the present invention makes an explanation with embodiment preferably, be appreciated that concerning the professional of this area its all improvement is conspicuous after having read this specification sheets.Therefore should be appreciated that, disclosed hereinly the present invention includes these and improve that they belong in the scope in the claims.

Claims

1, automobile fuel composition, said composition contain the fuel that is in a liquid state usually and are enough to keep the following additive of the some amount of whole inlet system cleaning in the gasoline boiling range:

(A) the following amino-phenol of chemical formula:

Each A is respectively H or alkyl in the formula, and each T is respectively that H or carbonatoms are no more than about 28 alkyl, and a, b and c are respectively separately and equal 1 integer at least, and condition is a, and b and c sum are no more than the unsaturation valence link number of Ar; Ar is for having 0 to 3 substituent single ring, condense polycyclic ring or connecting polycyclic ring aromatics composition, and these substituting groups are optional from the one group of group that mainly is made of following groups:: figure forges overgrown with grass and bushes (25) lower alkoxy, nitro, carboxyl low-grade alkyl, nitroso-group, halogen and 2 kinds or multiple above-mentioned optional substituent combination:

(B) the following amine of general formula:

R in the formula ¹For containing about 8 alkyl, R to about 24 carbon atoms ²And R ³Be respectively H separately, contain 1 alkyl, perhaps the following group of general formula to about 24 carbon atoms:

R in the formula ⁵For containing 2 alkylidene groups, R to about 8 carbon atoms ²And R ³As front definition, each R ⁴Respectively for to contain 2 alkylidene groups to about 8 carbon atoms, each x, y and z respectively are 0 to about 20 integer.

2, composition as claimed in claim 1, wherein respectively do for oneself H or carbon atom quantity of each A is no more than about about 18 alkyl or alkenyl.

3, composition as claimed in claim 2, wherein having 1 A at least is not H.

4, composition as claimed in claim 1 wherein has at least 1 A on average to contain 9 to the alkyl that is no more than about 750 aliphatic carbon atoms.

5, composition as claimed in claim 4, alkyl A wherein is pure hydro carbons.

6, composition as claimed in claim 5, alkyl A wherein are to contain about 30 alkyl or alkenyls to about 400 carbon atoms, and this group is by the C of homopolymerization or copolymerization _2-10Alkene obtains.

7, composition as claimed in claim 6, wherein said C _2-10Alkene is selected from C _2-101-alkene and composition thereof.

8, composition as claimed in claim 7, wherein said 1-alkene is selected from ethene, propylene, butylene, and composition thereof.

9, composition as claimed in claim 1 does not wherein have available substituting group on the Ar, b and c are 1, and it is alkyl that 1 A is arranged.

10, composition as claimed in claim 1, wherein respectively do for oneself H or alkyl or alkenyl of each T.

11, composition as claimed in claim 1, amino-phenol wherein (A) has following chemical formula:

R ' on average contains about 30 to about 400 aliphatic carbon atoms for the group based on saturated substantially hydrocarbon in the formula; R is " for being selected from a member with next group group: low alkyl group, lower alkoxy, carboxyl low-grade alkyl, nitro, nitroso-group and halogen; P is 0 or 1.

12, composition as claimed in claim 1, alkyl R wherein is alkyl or alkenyl.

13, composition as claimed in claim 12, X wherein are 0 or 1.

14, composition as claimed in claim 13, Y wherein and Z are zero.

15, composition as claimed in claim 12, X wherein are zero, have at least one to be 1 to about 5 integer among Y and the Z.

16, composition as claimed in claim 15, wherein Y and Z sum about from 1 to 15.

17, composition as claimed in claim 14, X=1 wherein.

18, composition as claimed in claim 1, wherein each R ⁴Be respectively and contain 2 alkylidene groups to about 3 carbon atoms.

19, composition as claimed in claim 14, R wherein ²And R ³Be H, X=0.

20, composition as claimed in claim 1, wherein (A) and weight ratio (B) are about 150: 1 to about 1: 100.

21, composition as claimed in claim 1 for per 1000 barrels of fuel, contains 10 (A) and about 1 (B) to about 100 pound weight to about 150 pound weight that have an appointment in the said composition.

22, composition as claimed in claim 1 wherein also contains a kind of liquid agent oil (C).

23, composition as claimed in claim 22, liquid agent oil wherein is mineral oil.

24, composition as claimed in claim 20 also contains liquid agent oil (C) in the said composition, its weight ratio (A): (C) be about 1: 20 to about 3: 1.

25, composition as claimed in claim 21 for per 1000 barrels of fuel, also contains the 30 liquid agent oil (C) to about 150 pound weight of having an appointment in the said composition.

26, the method for whole inlet system cleaning in the oil engine of maintenance with gasoline as fuel, this method comprises with the fuel of the described Fuel Petroleum composition of claim 1 as such engine.

27, the method for whole inlet system cleaning in the oil engine of maintenance with gasoline as fuel, this method comprises with the fuel of the described Fuel Petroleum composition of claim 2 as such engine.

28, the method for whole inlet system cleaning in the oil engine of maintenance with gasoline as fuel, this method relates to the fuel of the described Fuel Petroleum composition of claim 24 as such engine.

29, be used for port fuel and inject, with the automobile fuel composition of the oil engine of gasoline as fuel, said composition contains the fuel that is in a liquid state usually and is enough to prevent and reduces the following additive of the some amount that the intake valve deposition generates in the gasoline boiling range:

(A) the following amino-phenol of chemical formula:

Each A is respectively H or alkyl in the formula, and each T is respectively that H or carbonatoms are no more than the alkyl about 28, and a, b and c are respectively separately and equal 1 integer at least, and condition is a, and b and c sum are no more than the free valence mumber of unsaturation of Ar; Ar is for having 0 to 3 substituent single ring, condensing polycyclic ring or connecting-type polycyclic ring aromatics composition, these substituting groups are optional from the one group of group that mainly is made of following groups: low alkyl group, lower alkoxy, nitro, carboxyl low-grade alkyl, nitroso-group, halogen, and 2 kinds or the multiple above-mentioned substituent combination of selecting for use;

(B) the following amine of general formula:

30, composition as claimed in claim 29, wherein each A respectively is respectively that H or carbon atom quantity are no more than alkyl or the alkenyl about 18.

31, composition as claimed in claim 30, wherein having an A at least is not H.

32, composition as claimed in claim 29 wherein has an A at least on average to contain 9 to the alkyl that is no more than about 750 aliphatic carbon atoms.

33, composition as claimed in claim 32, alkyl A wherein is pure hydro carbons.

34, composition as claimed in claim 33, alkyl A wherein are to contain about 30 alkyl or alkenyls to about 400 carbon atoms, and this group is by the C of homopolymerization or copolymerization _2-10Alkene obtains.

35, composition as claimed in claim 34, wherein said C alkene is selected from by C _2-101-alkene and composition thereof.

36, composition as claimed in claim 35, wherein said 1-alkene is selected from ethene, propylene, butylene, and composition thereof.

37, composition as claimed in claim 34, wherein A is on average containing the substituting group of at least 30 left and right sides aliphatic carbon atoms, and this substituting group is by homopolymerization or copolymerization C _2-101-alkene obtains.

38, composition as claimed in claim 37, wherein said 1-alkene is selected from ethene, propylene, butylene, and composition thereof.

39, composition as claimed in claim 29 does not have available substituting group on the Ar wherein, b and c are 1 respectively, and it is alkyl that an A is arranged.

40, composition according to claim 29, T wherein are H or alkyl or alkenyl.

41, composition as claimed in claim 29, amino-phenol wherein (A) has following chemical formula:

R ' on average contains and has an appointment 30 to about 400 aliphatic carbon atoms for the saturated substantially group based on hydrocarbon in the formula; R is " for being selected from a member of following groups group: low alkyl group, lower alkoxy, carboxyl low-grade alkyl, nitro, nitroso-group and halogen; P is 0 or 1.

42, composition as claimed in claim 29, alkyl R wherein is alkyl or alkenyl.

43, composition as claimed in claim 42, X wherein are zero or 1.

44, composition as claimed in claim 43, Y wherein and Z are zero.

45, composition as claimed in claim 42, X wherein are zero, have at least one to be about 1 to 5 integer among Y and the Z.

46, composition as claimed in claim 45, wherein Y and Z sum about from 1 to 15.

47, composition as claimed in claim 44, X=1 wherein.

48, composition as claimed in claim 29, wherein each R ⁴Be respectively and contain 2 alkylidene groups to about 3 carbon atoms.

49, composition as claimed in claim 44, R wherein ²And R ³Be H, X=0.

50, composition as claimed in claim 29, wherein (A) and weight ratio (B) are about 150: 1 to about 1: 100.

51, composition as claimed in claim 29 for per 1000 barrels of fuel, contains 10 (A) and about 1 (B) to about 100 pound weight to about 150 pound weight that have an appointment in the said composition.

52, composition as claimed in claim 29 wherein also contains a kind of liquid agent oil (C).

53, composition as claimed in claim 52, liquid agent oil wherein is mineral oil.

54, composition as claimed in claim 50 also contains liquid agent oil (C) in the said composition, weight ratio (A): (C) be about 1: 20 to about 3: 1.

55, composition as claimed in claim 51 for per 1000 barrels of fuel, also contains the 30 liquid agent oil (C) to about 150 pound weight of having an appointment in the said composition.

56, inject at port fuel, prevent in the oil engine with gasoline as fuel or reduce that intake valve deposition generates or form the method that sedimentary place is removed that this method comprises with the fuel of the described automobile fuel composition of claim 29 as such engine.

57, inject at port fuel, prevent in the oil engine with gasoline as fuel or reduce that intake valve deposition generates or form the method that sedimentary place is removed that this method comprises with the fuel of the described automobile fuel composition of claim 30 as such engine.

58, inject at port fuel, prevent in the oil engine with gasoline as fuel or reduce that intake valve deposition generates or form the method that sedimentary place is removed that this method is with the fuel of the described automobile fuel composition of claim 55 as such engine.

59, the method for the fuel delivery system of polluting in the oil engine of purification with gasoline as fuel, this system comprises port fuel injector and intake valve, this method is included in the following fuel of use in the internal combustion machine, and this fuel contains the fuel that is generally liquid in the gasoline boiling range; For per 1000 barrels of fuel, this fuel also contains has an appointment 200 to about 1000 pound weight:

(A) the following amino-phenol of chemical formula:

Each A is respectively H or the saturated substantially group based on hydrocarbon in the formula, and each T is respectively that H or carbonatoms are no more than the alkyl about 28, and a, b and c are respectively separately and equal 1 integer at least, and condition is a, and b and c sum are no more than the free valence mumber of unsaturation of Ar; Ar is for having 0 to 3 substituent single ring, condensing polycyclic ring or connecting-type polycyclic ring aromatics composition, these substituting groups are optional from the one group of group that mainly is made of following groups: low alkyl group, lower alkoxy, nitro, carboxyl low-grade alkyl, nitroso-group, halogen, and 2 kinds or the multiple above-mentioned substituent combination of selecting for use; For per 1000 barrels of fuel, this fuel also contains has an appointment 20 to about 100 pound weight

(B) the following amine of general formula:

60, method as claimed in claim 59, wherein for per 1000 barrels of fuel, fuel also contains the 200 liquid agent oil (C) to about 1000 pound weight of having an appointment.