CN103602355B

CN103602355B - For the treatment of the fuel dope of the inside deposition thing of fuel injector

Info

Publication number: CN103602355B
Application number: CN201310134999.4A
Authority: CN
Inventors: J.M.加兰特-福克斯; S.D.施瓦布; X.方
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2012-04-19
Filing date: 2013-04-18
Publication date: 2016-04-20
Anticipated expiration: 2033-04-18
Also published as: GB201307043D0; CN103602355A; BE1021686B1; GB2504371A8; GB2504371B; SG194314A1; GB2504371A

Abstract

A kind of fuel dope of the inside deposition thing for the treatment of fuel injector.A kind of method cleaning the intraware of fuel injector for diesel motor.Method comprises runs fuel injection diesel motor with a kind of fuel composition, described fuel composition comprise primary amount fuel and based on fuel composition gross weight about 10 to the compound of (A) following formula of about 100ppm weight and tautomer thereof and enantiomer, wherein R ²for having the alkyl of 100 to 5000 number-average molecular weights.

Description

For the treatment of the fuel dope of the inside deposition thing of fuel injector

related application

The application is that the part of the present co-pending application sequence number 12/119,788 that on May 13rd, 2008 submits to continues, and is the part continuation of the present co-pending application sequence number 13/111.364 that on May 19th, 2011 submits to.

Technical field

The disclosure relates to some diesel fuel additive, and relates to clean and/or prevent in the method running the inside deposition thing in the injector of engine for diesel oil fuel.Specifically, the disclosure relates to the method for the effectively inside deposition thing of antagonism in the injector of the engine for running with ultra low sulfur diesel fuel.

Background technology

Diesel oil fuel and the nearest change of diesel fuel additive have produced the relevant new injector performance problem of settling, comprise the utilization novel type settling that comparatively morning, diesel oil fuel preparation did not live through.Injector performance problem crosses over all links; Fleet, winning equipment, tillage equipment, railway and inland shipping engine on road.

Transport operators, fuel marketing personnel and manufacturers of engines now just witness the settling formed on the internal part of fuel injector.If do not processed, these settlings just can cause remarkable power loss, reduce fuel economy, increase fault-time in extreme circumstances and produce higher maintenance cost owing to changing " adhesion (stuck) injector " too early.Believe that new settling is that other that use in some common corrosion inhibitor, component of biofuel and acid friction modifiers or fuel reacts containing carboxyl group and micro-transition metal, alkali and alkaline earth metal ions, produce the result of salt more not easily molten in ultra-low-sulphur diesel (ULSD) fuel than in the past compared with high-sulfur fuel.When there is this type of salt in the fuel for high-pressure common rail (HPCR) engine design, salt can tend to the very close tolerance region (verytighttolerancearea) being deposited on injector.This type of settling can cause bad fuel injection, and bad fuel injection can cause power loss then, loses fuel economy, not smooth running engine, and finally causes too much vehicle break-down time and maintenance cost.

ULSD be equivalent to now the U.S. supply all distillate fuel about 79%.Recyclable fuel standard minimum quantity for biofuel was also increased to 1,000,000,000 gallons in 2012.There are indications, in fuel, use the amount of required biofuel higher in the future.Therefore, the fuel nomination list of change continues to shift to more biofuel (producing the Sediment Source that the another kind of material is possible in fuel system) in more ULSD (having less solvability for the salt that can generate) and market.

Summary of the invention

According to the disclosure, exemplary provides a kind of method cleaning the intraware of fuel injector for diesel motor.Method comprises runs fuel injection diesel motor with a kind of fuel composition, described fuel composition comprise primary amount fuel and based on fuel composition gross weight about 10 to the compound of (A) following formula of about 100ppm weight:

And tautomer and enantiomer, wherein R ²for having the alkyl of 100 to 5000 daltons number average molecular weight.

Another embodiment of the present disclosure provides the method for the amount of the salt deposit of a kind of minimizing on the intraware of the fuel injector for fuel injection diesel motor.Method comprises runs diesel motor with a kind of fuel composition, and described fuel composition comprises the compound of the fuel of primary amount and (A) following formula of minor amount:

Another embodiment of the present disclosure provides a kind of method preventing the fuel filter for the fuel injector of fuel injection diesel motor from blocking.Method comprises the compound of (A) following formula of fuel and the minor amount providing primary amount:

And tautomer and enantiomer, wherein R ²for having the alkyl of 100 to 5000 daltons number average molecular weight, and (B) a certain amount of hydrocarbyl succinimide dispersion agent; Wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And make fuel flow through fuel filter for fuel injector.

The advantage of fuel dope described herein is, additive not only can reduce the amount of the inside deposition thing formed in direct and/or indirect diesel fuel injectors, and additive also effectively can clean dirty fuel injector, and the obstruction of fuel filter in the supply of fuel of fuel injector can be prevented.

Other embodiments of the present disclosure and advantage can part be set forth in the following discussion, and/or are familiar with by implementing the disclosure.Should be appreciated that, aforementioned general description and following detailed description are all only exemplary and illustrative, are not such to restriction of the present disclosure as claimed.

Specifically, the disclosure relates to following embodiment:

1. one kind is cleaned the method for the intraware of the fuel injector for diesel motor, described method comprises runs fuel injection diesel motor with a kind of fuel composition, described fuel composition comprise primary amount fuel and based on fuel composition gross weight about 10 to the compound of (A) following formula of about 500ppm weight:

2. the method for clause 1, wherein R ²for having the polyisobutene of about 200 to about 3,000 daltons number average molecular weight.

3. the method for clause 1, wherein fuel injection diesel motor comprises direct fuel injection diesel motor.

4. the method for clause 1, comprise (B) a certain amount of hydrocarbyl succinimide dispersion agent further, wherein in fuel, the weight ratio of A:B is 1:2 to 1:10.

5. the method for clause 4, wherein hydrocarbyl succinimide dispersion agent comprises the reaction product of polyalkenyl amber acid or anhydride and tetren.

6. the method for clause 5, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

7. the method for clause 6, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more terminal ethylenic double bond.

8. the method for clause 4, wherein fuel package is containing the mixture of A and B of 50 to 500ppm weight.

9. one kind is reduced the method for the amount of the salt deposit on the intraware of the fuel injector for fuel injection diesel motor, described method comprises runs diesel motor with a kind of fuel composition, and described fuel composition comprises the compound of the fuel of primary amount and (A) following formula of minor amount:

And tautomer and enantiomer, wherein R ²for having the alkyl of 100 to 5000 number-average molecular weights.

10. the method for clause 9, wherein fuel package containing based on fuel composition gross weight about 10 to the compound (A) of about 100ppm weight.

The method of 11. clauses 9, wherein R ²for having the alkyl of about 200 to about 3000 daltons number average molecular weight.

The method of 12. clauses 9, wherein fuel injection diesel motor is that direct fuel sprays diesel motor.

The method of 13. clauses 9, wherein fuel is ultra low sulfur diesel fuel.

The method of 14. clauses 9, comprise (B) a certain amount of hydrocarbyl succinimide dispersion agent further, wherein in fuel, the weight ratio of A:B is 1:2 to 1:10.

The method of 15. clauses 14, wherein hydrocarbyl succinimide dispersion agent comprises the reaction product of polyalkenyl amber acid or anhydride and tetren.

The method of 16. clauses 15, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

The method of 17. clauses 16, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more terminal ethylenic double bond.

The method of 18. clauses 14, wherein fuel package is containing the mixture of A and B of 50 to 500ppm weight.

19. 1 kinds of methods preventing the fuel filter for the fuel injector of fuel injection diesel motor from blocking, described method comprises the mixture of following (A) and (B) providing the fuel of primary amount and minor amount: the compound of (A) following formula

And tautomer and enantiomer, wherein R ²for having the alkyl of 100 to 5000 daltons number average molecular weight; (B) a certain amount of hydrocarbyl succinimide dispersion agent; Wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And

Fuel is made to flow through fuel filter for fuel injector.

The method of 20. clauses 19, wherein fuel filter has 2 micron openings for fuel flowing.

The method of 21. clauses 19, wherein fuel package is containing compound (the A)/Kg fuel being about 5mg to about 200mg based on active benchmark.

The method of 22. clauses 19, wherein fuel package is containing compound (the A)/Kg fuel of about 20mg to about 120mg.

The method of 23. clauses 19, wherein fuel package is containing ultra-low-sulphur diesel (ULSD) fuel.

Accompanying drawing explanation

Fig. 1 is the graphic representation of the exhaust casing temperature of passing in time when fuel dope on-test for four cylinder diesel motors.

Fig. 2 is the graphic representation of the exhaust casing temperature not using fuel sanitising agent to pass in time after 8 h run for four cylinder diesel motors.

Fig. 3 and 4 is the graphic representation (prior art) of the exhaust casing temperature using conventional oil sanitising agents to pass in time for four cylinder diesel motors.

Fig. 5 and 6 is the graphic representation of the exhaust casing temperature using the fuel sanitising agent of embodiment of the present disclosure to pass in time for four cylinder diesel motors.

Fig. 7 is the graphic representation fuel sanitising agent of a four cylinders embodiment of the present disclosure used for diesel engine being cleaned to the exhaust casing temperature of passing in time of dirty fuel injector.

Specific embodiments

Composition of the present disclosure (A) can minor amount be used in the diesel oil fuel of primary amount, and by the amine compound of following formula or its salt

(wherein R is selected from hydrogen and comprises the alkyl of about 1 to about 15 carbon atom, R ¹be selected from hydrogen and comprise the alkyl of about 1 to about 20 carbon atom) with the hydrocarbyl oxycarbonyl based compound of following formula

(wherein R ²for having the alkyl of about 200 to about 3000 daltons number average molecular weight) react and prepare.Undesirably limit by Theoretical Considerations, believe that the reaction product of amine and hydrocarbyl oxycarbonyl based compound is aminotriazole, the bis-amino triazole compounds of such as following formula

Comprise the tautomer with about 200 to about 3000 daltons number average molecular weight.The five-ring of triazole thought aromatics.Aminotriazole is to oxygenant quite stable, and pole hydrolysis.Although uncertain, believe that reaction product is the two-3-amino-1,2,4-triazole of polyalkenyl.

Term used herein " alkyl " uses with general significance well known to those skilled in the art.Specifically, " alkyl " refers to a kind of group, has the carbon atom being directly connected to molecule rest part, and has dominant hydrocarbon character.The example of alkyl comprises:

(1) hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituting group, with aromatics-, the aromatic substituent of aliphatic series-and alicyclic-replace, and the wherein cyclic substituents (such as, two substituting groups form alicyclic group together) that completed by another part of molecule of ring;

(2) hydrocarbon substituent be substituted, namely containing the substituting group of non-hydrocarbon, under this specification sheets linguistic context, this non-hydrocarbon does not change dominant hydrocarbon substituent (such as halogeno-group (especially chloro and fluoro), hydroxyl, alkoxyl group, sulfydryl, alkylthio, nitro, nitroso-group and sulphur oxygen base (sulfoxy));

(3) assorted substituting group, that is, while there is main dominant hydrocarbon character, under this specification sheets linguistic context, otherwise the substituting group of atom in the ring be made up of carbon atom or chain beyond carbon containing.Heteroatoms comprises sulphur, oxygen, nitrogen, and relates to the substituting group of such as pyridyl, furyl, thienyl and imidazolyl.General exist no more than two or there is the substituents of no more than as other example for every 10 carbon atoms in alkyl; In some embodiments, in alkyl, substituents is not had.

Should be understood that " biorenewable fuel " used herein and " biodiesel fuel " refer to any fuel obtained from the resource beyond oil.These resources include but not limited to cereal, corn, beans and other farm crop; Grass, such as switchgrass, awns belong to and hybrid grass; Algae, sea grass, vegetables oil; Natural fat; And composition thereof.In one aspect, biorenewable fuel can comprise single hydroxyl alcohol, such as, comprise those alcohol of 1 to about 5 carbon atom.The unrestricted example of the single hydroxyl alcohol be applicable to comprises methyl alcohol, ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol and primary isoamyl alcohol.

Should be understood that term used herein " primary amount " refers to the amount being more than or equal to 50% weight relative to the gross weight of composition, such as about 80 to about 98% weight.Should be understood that term used herein " minor amount " refers to the amount being less than 50% weight relative to the gross weight of composition in addition.

Should be understood that term used herein " salt or salt deposit " refers to metal carboxylate.

amine compound

The applicable amine compound of following formula

Guanidine and aminoguanidine or its salt, wherein R and R can be selected from ¹be defined as above.Therefore, amine compound can be selected from the inorganic salt of guanidine, the halogenide of such as guanidine, carbonate, nitrate, phosphoric acid salt and orthophosphoric acid salt.Term " guanidine " refers to guanidine and guanidine derivative, such as aminoguanidine.In one embodiment, the guanidine compound for the preparation of additive is aminoguanidine bicarbonate.Aminoguanidine bicarbonate can be easy to obtain from commercial sources, or can well-known way preparation.

hydrocarbyl oxycarbonyl based compound

The hydrocarbyl oxycarbonyl radical reaction immunomodulator compounds of additive can for having hydrocarbyl portion and carbonyl moiety and can being combined into any suitable combination thing of additive of the present disclosure with amine compound.The unrestricted example of the hydrocarbyl oxycarbonyl based compound be applicable to includes but not limited to the ester of succinyl oxide, the succsinic acid of alkyl replacement and the succsinic acid of alkyl replacement that alkyl replaces.

In some respects, hydrocarbyl oxycarbonyl based compound can for having the polyalkylene succinic anhydride reagent of following formula:

Wherein R ²for hydrocarbyl portion, such as, there is the polyalkenyl group of about 100 to about 5,000 number-average molecular weights.Such as, measured by GPC, R ²number-average molecular weight can be about 200 to about 3,000 dalton.Except as otherwise noted, the molecular weight in this specification sheets is number-average molecular weight.

R ²polyalkenyl group can comprise and is one or morely selected from polymer unit that is linear or branched alkene group unit.In some respects, alkenyl units can have about 2 to about 10 carbon atoms.Such as, polyalkenyl group can comprise and is one or morely selected from the linear of ethylene group, propylidene group, butylene, pentylidene group, hexylen radical, octylene group and sub-decyl group or branched polymer unit.In some respects, R ²polyalkenyl group can be the form of such as homopolymer, multipolymer or terpolymer.In one aspect, polyalkenyl group is isobutylene.Such as, polyalkenyl group can be the homopolymer of polyisobutene, comprises about 10 to about 60 isobutylenes, such as about 20 to about 30 isobutylenes.For generating R ²the polyalkenyl compound of polyalkenyl group generates by any applicable method, such as, by the Conventional catalytic oligomerization of alkene.

In yet another aspect, hydrocarbyl portion R ²can derived from the linear alhpa olefin by preparing in the ethylene oligomerization reaction of method well known in the art or acid isomerization alhpa olefin.These hydrocarbyl portions can have about 8 carbon atoms to more than 40 carbon atoms.Such as, the alkenyl part of this type can derived from linear C ₁₈alhpa olefin or C _20-24the mixture of alhpa olefin or derived from acid isomerization C ₁₆alhpa olefin.

In some respects, the available highly reactive polyisobutenes with the polymer molecule of relatively a high proportion of tool terminal vinylidene generates R ²group.In an example, polyisobutene comprise terminal ethylenic double bond at least about 60% (such as, about 70% to about 90%).Industrially generally trend towards changing into highly reactive polyisobutenes, the highly reactive polyisobutenes known is disclosed in such as U.S. Patent number 4,152,499, and its disclosure is incorporated herein by reference in full.

The specific examples of hydrocarbyl oxycarbonyl based compound comprises such as dodecenyl succinic anhydride, C _16-18the compound of alkenyl succinic anhydride and polyisobutenyl succinic anhydride (PIBSA).In some embodiments, PIBSA can have vinylidene content about 4% to the polyisobutene part being greater than about 90%.In some embodiments, in hydrocarbyl oxycarbonyl based compound, carbonyl number and the ratio of hydrocarbyl portion number can be about 1:1 to about 6:1.

In some respects, about 1 mol maleic anhydride can be reacted by every mole of polyalkylene, make the polyalkylene succinic anhydride obtained have each polyalkylene substituting group about 0.8 to about 1 succinyl oxide base.In other side, the weight ratio of succinic anhydride group and alkylidene group in the scope of about 0.5 to about 3.5, such as, about 1 to about 1.1.

Hydrocarbyl oxycarbonyl based compound can be prepared with any appropriate methodology.Generate the method for hydrocarbyl oxycarbonyl based compound well known.The example generating the currently known methods of hydrocarbyl oxycarbonyl based compound comprises blending polyolefins and maleic anhydride.Polyolefine and maleic anhydride reagent are heated to the temperature of such as about 150 DEG C to about 250 DEG C, optionally use catalyzer, such as chlorine or superoxide.The another kind of illustrative methods preparing polyalkylene succinic anhydride is described in U.S. Patent number 4,234,435, and described full patent texts is incorporated herein by reference.

Above-mentioned hydrocarbyl oxycarbonyl based compound and amine compound can be mixed together under the proper conditions, to provide required product amino-triazole compound thing of the present disclosure.In one of the present disclosure, can to the alkyl carbonyl of about 1:2.5 and the mol ratio of amine, reaction agent compounds be mixed together by about 1:1.Such as, the mol ratio of reagent can be about 1:1 to about 1:2.2.

At barometric point, applicable temperature of reaction can be about 155 DEG C to about 200 DEG C.Such as, temperature of reaction can be about 160 DEG C to about 190 DEG C.Any applicable reaction pressure can be used, such as, comprise lower than atmospheric pressure or superatmospheric pressure.But, list when the temperature range pressure that can be different from beyond normal atmosphere reacts those.Reaction can be carried out about 1 little of about 8 hours sections, preferably little in the scope of about 6 hours about 2.

More of the present disclosure in, compound (A) can combinationally use with diesel oil fuel soluble carrier.These carriers can be all kinds, as liquid or solid, and such as wax.The example of liquid vehicle includes but not limited to mineral oil and oxygenatedchemicals (oxygenate), such as liquid poly-alkoxylation ether (also referred to as polyalkylene glycol or polyalkylene ether), liquid poly-alkoxylation phenol, liquid poly-alkoxylation ester, liquid poly-alkoxylation amine, and composition thereof.The example of oxygenatedchemicals carrier can be found in the U.S. Patent number 5,752,989 that on May 19th, 1998 authorizes Henly etc., and the explanation of those carriers is all incorporated herein by reference.The other example of oxygenatedchemicals carrier comprises the aryl poly-alkoxylation thing that alkyl replaces, and as described in the U.S. Patent Publication number 2003/0131527 of the Colucci that on July 17th, 2003 announces etc., it illustrates incorporated herein by reference in full.

In other respects, composition of the present disclosure can be free of carrier.Such as, the some compositions of the application can be free of mineral oil or oxygenatedchemicals, those oxygenatedchemicalss as previously discussed.

One or more other optional compound can be there are in the fuel composition of disclosed embodiment.Such as, fuel can comprise the cetane number improver, corrosion inhibitor, cold flow improver (CFPP additive), pour point reducer, solvent, demulsifying compound, slip additive, friction modifiers, amine stabiliser, combustion improving agent, dispersion agent, antioxidant, thermo-stabilizer, conductivity modifiers, metal passivator, labeling dye, organic nitrates ignition accelerator, cyclopentadienyl tricarbonyl manganese compound (cyclomaticmanganesetricarbonyl) etc. of convention amount.In some respects, composition described herein can comprise based on one or more of multifunctional additive for lubricating oils gross weight about 10% weight or less above additive, or in other side, about 5% weight or less.Similarly, fuel can comprise the conventional oil blending compound of suitable amount, such as methyl alcohol, ethanol, dialkyl ether etc.

Disclosed embodiment some in, can use organic nitrates ignition accelerator, comprising wherein aliphatic series or alicyclic group is saturated aliphatic series or alicyclic nitric ether, and comprises at most about 12 carbon atoms.The example of spendable organic nitrates ignition accelerator is methyl nitrate, ethyl nitrate, propyl nitrate, isopropyl nitrate, nitric acid allyl ester, Butylnitrate ester, isobutyl nitrate, the secondary butyl ester of nitric acid, the nitric acid tert-butyl ester, amyl nitrate, isoamyl nitrate, 1-Methylbutyl nitrate, nitric acid 3-pentyl ester, the own ester of nitric acid, nitric acid heptyl ester, nitric acid 2-heptyl ester, n-octyl nitrate, isooctyl ester nitrate, nitric acid 2-ethylhexyl, nitric acid ester in the ninth of the ten Heavenly Stems, decyl nitrate, nitric acid undecyl ester, nitric acid dodecyl ester, nitric acid ring pentyl ester, cyclohexyl nitrate, nitrate cyclohexyl, nitric acid cyclo-dodecyl ester, nitric acid 2-ethoxy ethyl ester, nitric acid 2-(2-ethoxy ethoxy) ethyl ester, nitric acid tetrahydrofuran base ester etc.Also the mixture of this kind of material can be used.

The example that can be used for the optional metals passivator be applicable to of the composition of the application is disclosed in the U.S. Patent number 4,482,357 promulgated on November 13rd, 1984, and its disclosure is incorporated herein by reference in full.This kind of metal passivator comprises such as salicylidene Ortho-Aminophenol, Disalicylidene ethylene diamine, two salicylidene propylene diamine and N, N'-bis-salicylidenes-1，2-diaminopropane.

The optional cyclopentadienyl tricarbonyl manganese compound be applicable to that can be used for the composition of the application comprises such as cyclopentadienyl tricarbonyl manganese, methyl cyclopentadienyl tricarbonyl manganese, indenyl manganese tricarbonyl and ethyicydopentadi etanyf group manganese tricarbonyl.Other example of the cyclopentadienyl tricarbonyl manganese compound be applicable to is disclosed in the U.S. Patent number 5 promulgated on November 19th, 1996, the U.S. Patent number 3,015 that on January 2nd, 575,823 and 1962 promulgates, 668, the disclosure of the two is incorporated herein by reference in full.

In one embodiment, fuel composition of the present disclosure can comprise the succinimide dispersants and the mixture that combines of said components (A) that (B) alkyl replaces.Term used herein " succinimide " refers to the complete reaction product of the reaction between the amber acid or anhydride (or as succinic acylating agent) that comprises and replacing from amine and alkyl, and be intended to comprise wherein product except from the reaction of amine and anhydride component or contact the type obtained imide bond except also can have the compound of acid amides and/or sat linkage.

Reacted by the ethylenically unsaturated hydrocarbons and maleic anhydride that first make molecular weight, the succinyl oxide that applicable alkyl replaces can be generated.The temperature of reaction of about 100 DEG C to about 250 DEG C can be used.

Utilize higher ethylenically unsaturated hydrocarbons, good result can be obtained at about 200 DEG C to about 250 DEG C.This reaction promotes by chlorination.

General alkene can include but not limited to polymkeric substance and the multipolymer of cracked wax olefin, linear alpha-olefin, branched alpha-olefins, light alkene.Alkene can be selected from ethene, propylene, butylene (such as, iso-butylene), 1-octene, 1-hexene, 1-decene etc.Available polymkeric substance and/or multipolymer can include but not limited to polypropylene, polybutene, polyisobutene, ethylene-propylene copolymer, ethene-isobutylene copolymers, propylene-isobutylene copolymers, ethene-1-decene multipolymer etc.

In of disclosed embodiment, the hydrocarbyl substituent of the succinyl oxide that alkyl replaces can derived from butene polymers, the polymkeric substance of such as iso-butylene.Those polyisobutene that the HR-PIB comprising from having at least about 60% the terminal vinylidene content of (such as, about 70% to about 90% and more than) for the polyisobutene be applicable to herein generates.The polyisobutene be applicable to can comprise uses BF ₃those polyisobutene of catalyst preparing.As measured by GPC, the number-average molecular weight of hydrocarbyl substituent can change in wide region, such as about 100 to about 5000, such as about 500 to about 5000 dalton.

Can use beyond maleic anhydride containing carboxyl reaction agent, such as toxilic acid, fumaric acid, oxysuccinic acid, tartrate, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, ethylmaleic anhydride, dimethyl maleic anhydride, ethyl toxilic acid, dimethyl maleic acid, hexyl toxilic acid etc., comprise corresponding carboxylic acid halides and rudimentary aliphatic ester.In reaction mixture, the mol ratio of maleic anhydride and alkene can extensively change.Therefore, mol ratio can change to about 1.5 from about 5:1, and such as about 3:1 to about 1:3, as another example, can use the maleic anhydride of stoichiometric excess, react completely to force.Unreacted maleic anhydride is removed by vacuum distilling.

Any multiple polyamines is utilized in the preparation of the succinimide dispersants that can replace at alkyl.Non-limiting exemplary polyamines can comprise aminoguanidine bicarbonate (AGBC), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA) and heavy polyamines.Heavy polyamines can comprise the mixture of polyalkylene polyamine, there is a small amount of rudimentary polyamines oligopolymer (as TEPA and PEHA), but be mainly the oligopolymer with seven or more nitrogen-atoms, two or more primary amine of per molecule and branch more more substantial than conventional polyamine mixture.The other unrestricted polyamines that can be used for preparing the succinimide dispersants that alkyl replaces is disclosed in U.S. Patent number 6,548,458, and its disclosure is incorporated herein by reference in full.In an embodiment of the present disclosure, polyamines can be selected from tetren (TEPA).

In one embodiment, dispersion agent can comprise the compound of following formula:

Wherein n represents the integer of 0 or 1 to 5, R ²for the hydrocarbyl substituent be defined as above.In one embodiment, n is 3, R ²for polyisobutenyl substituting group, the substituting group that such as polyisobutene of the terminal vinylidene content of (such as, about 70% to about 90% and more than) is derivative from having at least about 60%.The reaction product of the succinyl oxide (such as, polyisobutenyl succinic anhydride (PIBSA)) that the compound of previously described formula can replace for alkyl and polyamines (such as, tetren (TEPA)).

When preparing the fuel composition of the application, can be enough to reduce or suppress the amount that in diesel motor, settling is formed to use additive.In some respects, fuel can comprise the above-mentioned bis-amino triazole compounds controlling or reduce the minor amount forming engine deposits (injector deposits in such as diesel motor).Such as, the diesel oil fuel of the application can comprise and is about the bis-amino triazole compounds of 5mg to the amount of about 500mg bis-amino triazole compounds/Kg fuel based on activeconstituents benchmark, and such as about 20mg is to about 120mg bis-amino triazole compounds/Kg fuel.Utilize carrier in, fuel composition can comprise and is about the carrier of amount of 1mg to about 100mg carrier/Kg fuel based on activeconstituents benchmark, and such as about 5mg is to about 50mg dispersion agent/Kg fuel.Activeconstituents benchmark does not comprise the weight of following material: (i) combines and be retained in the unreacted components in the product of preparation and use, such as, and polyalkylene compound; (ii) in the preparation of bis-amino triazole compounds, between its Formation period or afterwards but the solvent that (if utilizing carrier) uses before adding carrier (if existence).

On the other hand, fuel composition of the present disclosure can comprise based on activeconstituents benchmark about 50 to the dispersion agent as herein described (B) of the amount of about 500ppm, such as, be about 80ppm to about 200ppm (weight) based on fuel composition gross weight.

Utilize carrier in, fuel composition can comprise and is about the carrier of amount of 10mg to about 1000mg carrier/Kg fuel based on activeconstituents benchmark, and such as about 25mg is to about 700mg carrier/Kg fuel.Activeconstituents benchmark does not comprise the weight of following material: (i) combines and be retained in the unreacted components in the disclosed additive of preparation and use; (ii) in the preparation of disclosed additive between its Formation period or afterwards but the solvent that (if utilizing carrier) uses before adding carrier (if existence).

The additive of the application, the optional additive comprising above-mentioned bis-amino triazole compounds and use in fuel formulations of the present invention, can mix base diesel fuel separately or with various sub-portfolio.In some embodiments, the binder component useful additives enriched material of the application mixes diesel oil fuel simultaneously, because when being multifunctional additive for lubricating oils form, this make use of the mutual consistency and facility that are provided by the combination of composition.Use enriched material also can reduce blending time, and reduce the possibility of fusion mistake.

Therefore, in certain embodiments, the application relates to a kind of diesel fuel additive, and described diesel fuel additive comprises bis-amino triazole compounds, and this compound is the reaction product of above-mentioned at least one guanidine and at least one polyalkylene succinic anhydride.Additive can comprise one or more of above listed other composition.Additive can through packaging, and to separate with diesel oil fuel with such as concentration form and sell.Then, can by client as required by additive and diesel oil fuel fusion.

The diesel oil fuel of the application can be used for fixing diesel motor (such as, engine for power generating equipment, pumping plant etc.) and on-fixed diesel motor (such as, being used as the engine of primover in automobile, truck, highway flattening apparatus, military vehicle etc.) both operations.Therefore, the aspect of the application relates to the method for the amount of the injector deposits of the diesel motor reducing the one or more direct fuel injectors having at least one combustion chamber and be communicated with combustion chamber fluid.In yet another aspect, also improvement can be observed in indirect diesel fuel injectors.In some respects, the compression ignition fuel based on hydrocarbon of the bis-amino triazole additive that method comprises comprising the application injects combustion chamber by the injector of diesel motor, and is lighted a fire by compression ignition fuel.In some respects, method also can comprise at least one in above-mentioned other composition is optionally mixed into diesel oil fuel.

In one embodiment, the diesel oil fuel of the application can substantially containing the succinimide dispersants compound that (such as completely without) is conventional.According to the application's intention, term " does not contain " concentration being defined as and injector degree of cleaning or settling formation not had in fact to detectable impact substantially.

The application another in, fuel dope can be free of or substantially containing 1,2,4-triazole beyond above-mentioned triazole.Such as, composition can not contain the triazole of formula II substantially,

Wherein R ⁴and R ⁵independently be selected from hydrogen and alkyl, its condition is R ⁴and R ⁵be not one of at least hydrogen.The example of alkyl comprises C ₂to C ₅₀linear, branch or cyclic alkyl; C ₂to C ₅₀linear, branch or cyclic alkenyl radical; Be substituted or unsubstituted aryl, such as phenyl, tolyl and xylyl.

Do not wish by theoretical restriction, believe that the inside salt deposit in fuel injector can be produced by the metal ion pollution in fuel.Metal ion from basic fuel itself, or can come from the additive putting into basic fuel.When existing, metal ion can (such as, corrosion inhibitor (such as, dodecyl succinate corrosion inhibitor) and/or the reaction of Biodiesel Fatty acid esters, to generate salt form settling with carboxylate salt (ester) sense fuel dope.Because modern injector manufactures poling close tolerance (extremelyclosetolerance), any this kind of settling all can move the intraware of serious limit injection device.Therefore, salt deposit can cause the significance loss of energy owing to clinging injector needle, reduces fuel economy, wasted power and increase discharge.Inside deposition thing is general not too general in common diesel fuel, but has found expression in ULSD fuel.Surprisingly, as described herein, find that component (A) is independent or combine clean with component (B) and/or prevent from fuel injector, generate this kind of inner salt deposit.

Embodiment

Following examples are the explanation of exemplary of the present disclosure.Local at other of these embodiments and the application, except as otherwise noted, all numbers and percentage ratio are all by weight.These embodiments are only intended in order to illustration purpose provides, and are not intended to limit scope of the present invention disclosed herein.

In the examples below, for high pressure co-rail diesel fuel system, assessing compound (A) and/or (A) add the impact of the additive of (B) on the diesel oil fuel polluted with carboxylate salt.Prove the tendency that fuel causes fuel injector to adhere also to prove that some fuel dope prevents or controls the ability of inside deposition thing in injector by testing of engine.With dynamometer engine test platform, the PeugeotDW10 diesel motor for running injector adherence test is installed.This engine is 2.0 liters of engines with four cylinders.Each combustion chamber has 4 valves, and fuel injector is the DI piezoelectric injector with EuroV classification.

Core code program is made up of following: make engine run through 8 h cycle, and allows engine soaking (soak) (tail-off) specified time measure.Then, for each cylinder, levy injector performance by measuring cylinder exhaust gas thermometer.If point at any time, the exhaust temperature of any cylinder more than 65 DEG C higher than other cylinder exhaust temperature any, just stops test, and thinks fault (one or more injector adhesion).If allowing after engine cool to envrionment temperature, 45 DEG C or larger temperature contrast in cold start-up display cylinder exhaust temperature, then also thinking and testing fault.Can also by take injector apart and subjective determine pin to remove from nozzle housing needed for power confirm the adhesion of pin and confirm fault thus.Degree of cleaning test is run for maintenance clean-up performance and clean-up performance.

The fuel of test before test prepares to comprise and rinses from engine, removes injector afterwards.Check test injector, cleaning, and be reinstalled in engine.If select new injector, then new injector is made to be circulated by break-in in 16 hours.Then, with required testing campaign program starting engine.Once engine gets hotter, just detection power under 4000RPM and full load, recovers for the full power after clean injector.If power detection result, in specification, just starts testing campaign.Be provided for following table 1 evaluating the performance circulated according to the DW10 adherence test of fuel dope of the present disclosure.

performance in 1 hour of table 1-DW10 adherence test circulation.

Step	Time length (minute)	Engine speed (rpm)	Load (%)	Moment of torsion (Nm)	Forced air (DEG C) after charge air cooler
						1	2	1750	20	62	45
2	7	3000	60	173	50
						3	2	1750	20	62	45
4	7	3500	80	212	50
						5	2	1750	20	62	45
6	10	4000	100	*	50
						7	2	1250	10	25	43
8	7	3000	100	*	50
						9	2	1250	10	25	43
10	10	2000	100	*	50
						11	2	1250	10	25	43
12	7	4000	100	*	50

embodiment 1 (injector adhesion testing of engine)

Diesel engine machine nozzle adherence test PeugeotDW10 engine carries out according to the code of table 1.For maintenance cleaner assay, the diesel oil fuel polluted with metal carboxylate is also used in the detergent additive operation engine indicated in embodiment.For cleaner assay, first run engine without detergent additive, to set up the baseline of adhesion fuel injector with the diesel oil fuel of metal carboxylate pollution.Then, engine is run by the equal fuel comprising shown detergent additive.In all tests, the fuel package of test is containing 200ppmv oilness properties-correcting agent and 1600ppmv cetane number improver, 20ppmw dodecyl succinate, 3ppmwNaOH and 25ppmwv water.In on-test, for all 4 cylinders, as shown in (Fig. 1), uniform exhaust temperature instruction does not have injector to adhere.But, the cold start-up display injector adhesion of engine after 8 hours, as shown in Figure 2.In all figure, curve A is cylinder 1, and curve B is cylinder 2, and curve C is cylinder 3, and curve D is cylinder 4.

comparing embodiment 2

In this embodiment, conventional succinimide dispersant additives is added to fuel with 75ppmw treatment rate.After Fig. 3 shows fuel 16 h run used containing typical cleaning agent, injector is adhered.

comparing embodiment 3

In this embodiment, quaternary ammonium salt diesel fuel additive suit is added to fuel with 75ppmw treatment rate.Fig. 4 display injector adhesion after this fuel 7 h run.

embodiment 4

Compound (A) is added to fuel with 75ppmw treatment rate.After 16 h run, Fig. 5 shows injector and does not all adhere.Physical examination injector after test completes, determines that injector is not all adhered.

embodiment 5

In this test, for the total treatment rate of 75ppmw, the compound (A) of 15ppmw and the compound (B) of 60ppmw are combined.After Fig. 6 is presented at 16 h run, injector is not all adhered.

embodiment 6

Prove that detergent additive cleans the ability of dirty fuel injector in this experiment.Total treatment rate of 50ppmw in for fuel, before adding the mixture of the compound (A) of 10ppmw and the compound (B) of 40ppmw, dirty fuel injector has the exhaust temperature being similar to Fig. 2.After Fig. 7 is presented at 8 h run, injector is not all adhered.

As shown in the previous embodiment, compare with conventional oil detergent additive, when with ULSD operating fuel engine, inclusion compound (A) or compound (A) add that the fuel dope of compound (B) significantly reduces the inside deposition thing in diesel fuel injectors.

It should be noted that, as used in this specification sheets and accessory claim, singulative " ", " being somebody's turn to do " and " described " comprise the indicator of plural number, unless specially and be clearly limited to an indicator.Term used herein " comprises " and grammatical variants is intended to for non-limiting, makes describing of project in enumerating not get rid of other similar items that can replace or be added to cited project.

For the intention of this specification sheets and additional claims, except as otherwise noted, the numeral of all expression amounts used in the specification and in the claims, percentage ratio or ratio and other numerical value is all interpreted as modifying by word " about " in all cases.Therefore, be contrary unless indicated, the digital parameters listed in specification sheets and accessory claim is approximation, can according to the desired properties change being sought by the disclosure to obtain.At bottom line, and do not limit application to the doctrine of equivalents of right as attempting, each digital parameters should at least according to reported significant figure numerical value and made an explanation by utilization ordinary rounding techniques.

Although describe specific embodiments, applicant or those skilled in the art can make and not predict at present or may unforeseenly to substitute at present, amendment, change, to improve and essentially equivalent thing.Therefore, being intended to comprise that all these substitute with revisable accessory claim, amendment, change, improving and essentially equivalent thing of submission.

Claims

1. one kind is cleaned the method for the intraware of the fuel injector for diesel motor, described method comprises runs fuel injection diesel motor with a kind of fuel composition, and described fuel composition comprises the fuel of (A) primary amount, (B) based on the compound of the following formula of fuel composition gross weight 10 to 500ppm weight:

And tautomer and enantiomer, wherein R ²for having the polyisobutentyl group of 100 to 5000 daltons number average molecular weight; With

(C) a certain amount of hydrocarbyl succinimide dispersion agent, wherein in fuel, the weight ratio of B:C is 1:2 to 1:10.

2. the process of claim 1 wherein R ²for having the polyisobutentyl group of 200 to 3,000 daltons number average molecular weight.

3. the process of claim 1 wherein that fuel injection diesel motor comprises direct fuel and sprays diesel motor.

4. the process of claim 1 wherein that hydrocarbyl succinimide dispersion agent comprises the reaction product of polyalkenyl amber acid or anhydride and tetren.

5. the method for claim 4, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

6. the method for claim 5, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more terminal ethylenic double bond.

7. the process of claim 1 wherein that fuel package contains the mixture of B and C of 50 to 500ppm weight.

8. one kind is reduced the method for the amount of the salt deposit on the intraware of the fuel injector for fuel injection diesel motor, described method comprises runs diesel motor with a kind of fuel composition, and described fuel composition comprises the compound of the fuel of (A) primary amount and the following formula of (B) 10 to 100ppm weight:

And tautomer and enantiomer, wherein R ²for having the polyisobutentyl group of 100 to 5000 number-average molecular weights; With

9. the method for claim 8, wherein R ²for having the polyisobutentyl group of 200 to 3000 daltons number average molecular weight.

10. the method for claim 8, wherein fuel injection diesel motor is that direct fuel sprays diesel motor.

The method of 11. claims 8, wherein fuel is ultra low sulfur diesel fuel.

The method of 12. claims 8, wherein hydrocarbyl succinimide dispersion agent comprises the reaction product of polyalkenyl amber acid or anhydride and tetren.

The method of 13. claims 12, wherein polyalkenyl amber acid or anhydride is derived from the polyisobutene with 800 to 1100 daltons number average molecular weight.

The method of 14. claims 13, wherein polyisobutene comprises the highly reactive polyisobutenes with at least 70% weight or more terminal ethylenic double bond.

The method of 15. claims 8, wherein fuel package is containing the mixture of B and C of 50 to 500ppm weight.

16. 1 kinds of methods preventing the fuel filter for the fuel injector of fuel injection diesel motor from blocking, described method comprises the compound of (A) following formula of fuel and the minor amount providing primary amount:

And tautomer and enantiomer, wherein R ²for having the polyisobutentyl group of 100 to 5000 daltons number average molecular weight; (B) mixture of a certain amount of hydrocarbyl succinimide dispersion agent, wherein in fuel, the weight ratio of A:B is 1:2 to 1:10; And wherein fuel package is containing compound (the A)/Kg fuel of 5mg to 200mg; And

Fuel is made to flow through fuel filter for fuel injector.

The method of 17. claims 16, wherein fuel filter has 2 micron openings for fuel flowing.

The method of 18. claims 16, wherein fuel package is containing compound (the A)/Kg fuel of 20mg to 120mg.

The method of 19. claims 16, wherein fuel package is containing ultra-low-sulphur diesel (ULSD) fuel.