CN87101878A - The fuel composition that is used for porous fuel injection system - Google Patents

The fuel composition that is used for porous fuel injection system Download PDF

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Publication number
CN87101878A
CN87101878A CN198787101878A CN87101878A CN87101878A CN 87101878 A CN87101878 A CN 87101878A CN 198787101878 A CN198787101878 A CN 198787101878A CN 87101878 A CN87101878 A CN 87101878A CN 87101878 A CN87101878 A CN 87101878A
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alkyl
fuel
aryl
polyglycol
oxidation
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亚伯拉罕·阿巴·齐默尔曼
约瑟夫·瓦尔迪
乔尔·罗伯特·西格尔
杰弗里·安东尼·坎顿
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Abstract

Described a kind of binder component, a kind ofly included the fuel composition of binder component and in porous fuel injection device, adopt fuel composition to reduce and/or prevent the method that injector stops up.This binder component comprises the demulsifying compound that amine that a kind of quilt is described especially and a kind of quilt are described especially.The best group compound comprises a kind of amine, a kind of amine oxide and a kind of demulsifying compound.

Description

The fuel composition that is used for porous fuel injection system
The present invention relates to a kind of fuel composition and using method thereof of anti-obstruction.Or rather, the present invention relates to the fuel composition that injector stops up in a kind of petrol engine that is specially adapted to reduce and/or prevents to be furnished with automatically controlled porous fuel injector.
In the past few years, the performance of oil engine is improved.Acquired one of the most significant improvement is exactly to use fuel injector to improve the performance of oil engine and the economy of fuel widely.When the vaporizer on being contained in oil engine was distributed to all cylinders by a manifold after with air and fuel mix, the fuel in the fuel-injection engine was sprayed into the manifold of each next-door neighbour's cylinder intake valve, in order to burning.Fuel injector system has two kinds of base types: mechanically controlled type and electronic control type.Early stage fuel injection type internal combustion engine adopts mechanically controlled type, i.e. the operation of each injector is by pressure controlled.Yet now, electronically controlled fuel injector had got widely and had used.In the electronically controlled fuel injector system, place the transmitter of venting port to be used for air and fuel ratio are remained in the narrow limit.Electronically controlled fuel injection system provides the identical performance that the mechanically controlled type fuel injection system can reach and the economic benefit of fuel, and can also accurately control fuel-air mixture, make catalyst oxidation-carbonoxide and hydro carbons generate carbonic acid gas thus, reduce oxynitride simultaneously, thereby satisfy the relevant rules of control discharging.Exhaust emission has been controlled in the certain strictness of the formulation of rules, thereby has caused the development of this new technology of electronically controlled fuel injector and application widely.
Have found that the hole opening degree of electronically controlled fuel injection system is very little, easily be deposited thing and stop up.Can determine that these settlings stop up to small part is caused by gasoline and oily vapour, all these occur in and are in close proximity to injector tip, behind tail-off, gasoline and oily vapour are condensed in the hot surface of injector pivot pin by roasting melting and center on the ring set surface of pivot pin.These settling fuel limitations flow in the specified cylinder, and the value that the sensor detecting that is contained in venting port is gone out is higher than needed oxygen and fuel ratio.Transmitter manages to correct this situation by the fuel quantity that increase is ejected in all cylinders.Can make the value of measuring on the venting port be higher than the ratio of needed fuel and air with that, then, transmitter manages to correct this situation by the fuel quantity that minimizing is ejected in each cylinder.In mixture scope too oil-poor and too rich oil, fuel is adjusted in this circulation and the air value causes bad vehicle traction performance often.In addition, tight gap of this novel injection device and the interior temperature of the higher shell that adopts at present also are easy to increase sedimental formation, thereby make vehicle drive force bad, and surpass the exhaust air pollution standards of emission control regulation.
Have found that gasoline scale remover commonly used can prevent or remove the throw out in the vaporizer effectively, occur in sedimental deposition in the electronically controlled fuel injection system but can not remove effectively and/or eliminate.At present removing sedimental feasible method from the fuel injector aperture generally comprises and mechanically removes injector or add than relatively large special additive fuel.Mechanical removal is the available whole injector of taking apart, the manual settling of removing, and also available polar solvent washes settling.But this method is unsatisfactory, and this is because cost is quite high and inconvenient.At present commercially available additive is not satisfactory especially, and this is because the description of product is pointed out, these additives will use with quite high concentration, and promptly per thousand barrels of fuel use about one to two ton additive.
For reducing and/or prevent the obstruction of eductor ports, or in order to make the useful commercial gasoline dope must be effective when the lower concentration, necessarily can not influence the combustionproperty of fuel excessively and necessarily can not besmirch catalyzer in the catalytic converter.
Additive has been added some characteristic of improving fuel in the gasoline.United States Patent (USP) the 3rd, 115, the structure that discloses the compound that uses No. 400
Figure 87101878_IMG5
Wherein R is a C 6～C 22Aliphatic hydrocarbyl, X are integers 2～4, and Y is to be an integer of 1 at least, and Z is to be an integer of 1 at least, and this compound is used to prevent or reduce carburettor icing.
United States Patent (USP) the 4th, 409 discloses for No. 000 and to be used for the mixture of common liq fuel as the dispersion agent of the oxyamine of engine and vaporizer scale remover and hydrocarbon dissolubility hydroxyl.The structural formula of compound is in disclosed oxyamine:
Figure 87101878_IMG6
R wherein 1Can be the alkyl that contains 8～30 carbon atoms, each R wherein 2, R 3, R 4And R 5Can be hydrogen, wherein a and b can be integers 1～75.
United States Patent (USP) the 4th, 231 discloses a kind of compound that uses for No. 883, and its structural formula is:
R wherein 1Be a kind of C 12～C 36Aliphatic hydrocarbyl, R 2And R 3Be 2 yuan of alkyl that contain 2～4 carbon atoms, X and Y are integers 1～4, and this compound is used for antifriction lubricating oil.Preferred compound comprises N, two (2-hydroxyethyl) alkylamines of N-.
United States Patent (USP) the 3rd, 387 relates to the nitrogen oxide that has replaced with organic for No. 953.Especially amine oxide prevents to get rusty, and as the deicing agent in the gasoline.This patent has provided the several representative general formula, and they contain following structural formula:
Figure 87101878_IMG8
Wherein: R 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl or substituted aryl; R 2And R 3Be identical or different C 1～C 24Alkyl, aryl, substituted alkyl or aryl, cycloaliphatic radical or heterocyclic radical.R 2And R 3Preferably include the alkyl that hydroxyl has replaced.Generally these compounds are joined in the gasoline, its concentration range is that per thousand barrels of gasoline (Ptb) approximately contain 2.0 to 100 pounds amine oxide.Two (2-hydroxyethyl) oxidation coconut amine is at the row of the additive of the best.
United States Patent (USP) the 3rd, 594,139 relate to a kind of antirust enriched material, and this material can be admixed all the year round with gasoline.This patent also discloses to use has preceding formula, as a kind of amine oxide of anti-gasoline dope use.This patent also discloses the optimized concentration that comprises two (2-hydroxyethyl) oxidation coconut amines.
Although these amine still are considered to the vaporizer scale remover, above-mentioned amine oxide also is used to antirust usually and prevents carburettor icing.
The amine oxide that also find to use hydroxyl to replace can cause additive losses, and this is because high water-soluble and cause in the adsorptivity of polar surfaces.
Thereby, need offer a kind of binder component of gasoline, this binder component will reduce effectively and/or eliminate obstruction, but not have tangible additive losses.
Also need to provide a kind of additive with demulsifying compound, this demulsifying compound will be effective when neutral and alkaline water exist.
Correspondingly also need to provide a kind of gasoline dope component, this binder component is quite cheap, and can effectively reduce and/or eliminate injector and stop up under lower concentration.
Also need to provide a kind of gasoline to add component, this binder component does not corrode catalyzer, and is harmless, and do not influence the combustionproperty of fuel.
Also need to provide a kind of gasoline dope component, this additive store with allocating system during easily active addition to becoming to engage in the gasoline.
The present invention relates to a kind of fuel composition, be used to reduce and/or prevent the injector obstruction that the automatically controlled fuel-injection engine of porous is interior.Said composition comprises:
A: gasoline
B: a kind of anti-plugging agent, its structural formula is:
Figure 87101878_IMG9
R wherein 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl or substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl, aryl, cycloaliphatic radical or heterocyclic radical; And,
C. demulsifying compound is selected from:
ⅰ. the acidylate polyglycol
ⅱ. alkylaryl sulphonate, polyglycol, alkoxide alkylphenol-aldehyde resins;
ⅲ. alkoxide alkylphenol-aldehyde resins and polyglycol; And,
ⅳ. the alkoxide alkyl phenolic resin; And their mixture.
In said composition, preferred R 1Be C 6～C 20Alkyl, or alkylated aryl, R 2And R 3Be respectively C 1～C 12The alkyl that hydroxyl has replaced.In preferred composition, R 1Comprise the C that from lipid acid, derives 8～C 18Substituting group.Preferred additives is selected from two (2-hydroxyethyl) coconut amines, two (2-hydroxyethyl) Tallow, beef amine, two (2-hydroxyethyl) stearylamide, two (2-hydroxyethyl) oleyl amine and composition thereof.Optimum addn is two (2-hydroxyethyl) coconut amines.Anti-plugging agent concentration in the fuel usually can be between about 2 to about 200ppm, and (is the weight percent of benchmark with the fuel composition gross weight) is preferably between about 20 to about 80ppm.The active concentration of demulsifying compound can be preferably between about 1.0 to about 8ppm between about 0.1 to about 20ppm.A kind of preferred demulsifying compound is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylphenol-aldehyde resins and polyglycol; And,
ⅲ. alkoxide alkylphenol-aldehyde resins and composition thereof.
Fuel dope also can comprise second kind of anti-plugging agent of amine oxide, and it has following structural:
Figure 87101878_IMG10
R wherein 4Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl, substituted aryl; R 5And R 6Be respectively C 1～C 24Alkyl, aryl, substituted alkyl or aryl, cycloaliphatic radical, heterocyclic radical and composition thereof; And,
The preferred anti-plugging agent of amine oxide includes such compound, wherein R 4Be C 6～C 20Alkyl or alkylated aryl; R 5And R 6Be respectively the C that hydroxyl has replaced 1～C 12Alkyl.The optimizing compound is R 1Comprise a kind of C 8～C 18Substituent compound.Best, the amine oxide additive is selected from (2-hydroxyethyl) oxidation coconut amine, two (2-hydroxyethyl) oxidation stearylamide, cacodyl oxide base coconut amine, and the oxide compound of dimethyl hydrogenation Tallow, beef amine, the oxide compound of dimethyl hexadecyl amine, and composition thereof.The anti-plugging agent of optimum oxidation amine is two (2-hydroxyethyl) oxidation coconut amines.
Fuel composition (as gasoline) can further comprise usually:
A. about 2 to about 200ppm two (2-hydroxyethyl) coconut amines; And,
B. about demulsifying compound of 0.1 to about 20ppm, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkoxide alkylphenol-aldehyde resins;
ⅲ. alkoxide alkylphenol-aldehyde resins and polyglycol; And,
ⅳ. the alkoxide alkylphenol-aldehyde resins; And composition thereof.
Preferred fuel composition comprises:
A. about 20 to about 120ppm two (2-hydroxyethyl) coconut amines; And,
B. about demulsifying compound of 1 to about 12ppm, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkoxide alkylphenol-aldehyde resins;
ⅲ. alkoxide alkylphenol-aldehyde resins and polyglycol; And,
ⅳ. the alkoxide alkylphenol-aldehyde resins; And composition thereof.
Preferred fuel composition also can comprise about 4 to about 40ppm two (2-hydroxyethyl) oxidation coconut amines.
A kind of preferred fuel multifunctional additive for lubricating oils that is used for oil engine, it comprises:
A. about 5 to about 60%(weight) two (2-hydroxyethyl) coconut amines;
B. about 0.25 to about 10%(weight) demulsifying compound, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkoxide alkyl phenolic resin;
ⅲ. alkoxide alkylphenol-aldehyde resins and polyglycol; And,
ⅳ. the alkoxide alkylphenol-aldehyde resins; And composition thereof, and
C. about 40 to about 95%(weight) solvent.
Fuel additive concentrate also can comprise about 1 to about 15%(weight) two (2-hydroxyethyl) oxidation coconut amines.
Preferred solvent comprises a kind of alkyl aromatic hydrocarbon solvent, as dimethylbenzene and a kind of C 4+ alcohol is preferably C 4～C 12Alcohol is preferably C 8Pure and mild the best is C 8Oxo alcohol.When water surpasses approximately 0.05 for the concentration ratio of amine oxide, also should add entry and the high alcohol of hydrocarbon dissolubility, be preferably Virahol.
The invention still further relates to a kind of method that is used for the electronically controlled fuel injection system of oil engine, this method comprises fuel is input to above-mentioned fuel injection system, and fuel comprises a kind of additive of significant quantity, and this additive comprises:
Figure 87101878_IMG11
R wherein 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl or substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl, aryl, cycloaliphatic radical or heterocyclic radical.R 2And R 3Be preferably the hydroxyl substituent.
The present invention relates to a kind of fuel composition, a kind of gasoline dope component and a kind of fuel composition is delivered to the method for fuel injection system has found that said composition reduces especially effectively and/or eliminates injector and stop up in injection system.The fuel that the present invention relates to comprises:
A. gasoline;
B. anti-plugging agent, its structural formula is as follows:
Figure 87101878_IMG12
R wherein 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl, substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl or aryl, cycloaliphatic radical, heterocyclic radical, and composition thereof; And,
C. demulsifying compound, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkoxide alkylphenol-aldehyde resins;
ⅲ. alkoxide alkylphenol-aldehyde resins and polyglycol; And,
ⅳ. the alkoxide alkylphenol-aldehyde resins; And composition thereof.
Preferred anti-plugging agent comprises such compound, wherein R 1Be C 6～C 20Alkyl or alkylated aryl; R 2And R 3It is respectively the agent alkyl that hydroxyl has replaced.The optimizing compound is R wherein 1Comprise a kind of C 8～C 18Substituent compound.Preferred additives is selected from two (2-hydroxyethyl) coconut amines, two (2-hydroxyethyl) stearylamide, two (2-hydroxyethyl) oleyl amine and composition thereof.These additives are according to known prepared, as are disclosed in United States Patent (USP) the 2nd, 541, and No. 678 method is utilized as a reference at this.Best anti-plugging agent is two (2-hydroxyethyl) coconut amines.
Found that amine oxide is effective as anti-plugging agent.When these compounds were extracted the water-content that becomes to contain in various degree, these compounds also offered the fuel rust-resisting property.These compounds have following structural formula:
Figure 87101878_IMG13
R wherein 4Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl, substituted aryl; R 5And R 6Be respectively C 1～C 24Alkyl, aryl, substituted alkyl or aryl, cycloaliphatic radical, heterocyclic radical and composition thereof.
Therefore, these oxidative amination compounds mix with aforementioned amine to use can provide a kind of effective anti-occlusion group compound, and rust-resisting property can be provided.The prepared that these amine oxides can be familiar with people, as be disclosed in United States Patent (USP) the 3rd, 387, the technology on No. 953.
Here, amine and amine oxide mix use as anti-plugging agent, when the concentration of amine oxide, between about 2 to about 80ppm, preferable range is when about 4 arrive between about 40ppm, usually, the concentration of amine will be between about 2 to about 200ppm, between the preferable range about 16 to about 100ppm.
Usually amine oxide contains the water that brings from manufacturing process.In the time might removing most of water, water be removed quite low content, promptly the ratio about 0.02 of water and amine oxide is to about 0.04, and this has just brought complicacy to manufacturing process.Amine oxide is generally Virahol as moisture commercially available with solution solvent.Have found that,, produced a kind of three-phase system, two organic phases, a water when a kind of enriched material that comprises above-mentioned amine oxide solution and a kind of when containing the solvent of anti-emulsion and oil-cell bottom after gasoline and the off-test mixing.
It is unfavorable forming two organic layers, because found this will cause amine oxide at two interlayers uneven distribution.In addition, second layer organic layer (this layer has higher amine oxide concentration) is easy to adhere to from the teeth outwards, thus the potentiality pollution that causes the loss of additive and may contact the follow-up hydrocarbon product on these surfaces.Have found that and use higher alcohols, be preferably C 4～C 17Alcohol, the best is C 8Oxo alcohol displacement Virahol part can reduce the possibility that forms two organic layer systems.When the mixture of amine and amine oxide also can reduce the formation of two kinds of organic phases, recommend this solvent to comprise a kind of aforesaid C 4～C 12Alcohol is with the possibility of two kinds of organic phases formation of further reduction.
Usually all adopt a kind of enriched material of amine and amine oxide, also comprise about 40 to about 95%(weight) solvent.The preferred compositions content range is as follows:
Component concentration scope (weight %)
Amine 8～32
Amine oxide 2～8
Solvent
Dimethylbenzene 30～80
C～C alcohol 2～20
Virahol 2～16
Water 0.2～1.5
Demulsifying compound 1～4
Following comparison example and embodiment have shown the obstruction of using anti-plugging agent to reduce and/or eliminate fuel injector.In below the comparison example and embodiment, the octane value of the fuel that is adopted is defined as follows:
(theoretical octane value+engine octane number)/2
Comparison example 1
In this test; drive three and have electronically controlled, fuel injection, 3.8 liters; the oil engine of 6 cylinders (1985 oldsmobile 98 ' s); adopt washing agent commercially available, that have the about 32ppm weight of fuel of concentration, unleaded, 87 octane value reference fuels; with following drive cycle, travel about 3500 miles: the urban district type travelled, shuts down 0.5 hour; road running 0.5 hour was shut down 0.5 hour.The motivating force of four cars all becomes worse and worse.92 octane value lead-free fuels with these automobile-used commercially available premium grade travel 300 miles then, and described fuel contains the scale remover that 2.5 times above-mentioned reference fuel is used.Motivating force is no change still.The data presentation of table I goes out fuel flow and still has obvious reduction below, and this shows both makes that scale remover does not exert an influence to high-load settling yet under high purification degree of building.Under predetermined standard conditions, comprise fuel pressure, pulse width and the cycle of operation, by the measurement branch rate that the stereometry fuel flow of solvent oil of injector reduces of flowing through.The percentage that reduces calculates with following formula:
Reduce %=(V clean-V is dirty)/(V is clean) * 100%
Wherein the clean and V of V is dirty is the measurement volumes of pure and the fuel injector solvent oil made dirty of flowing through.
Table 1
The flow of the injector holes of flowing through reduces percentage
Cycle # 123456
- - - - - -
Car A 11 12 35 30 7 10
Car B 79 12 38 9 14
Car C 22 11 28 4 11 10
Typical new-type 220021
Injector
As seen from Table 1, this commonly used and known vaporizer scale remover are invalid to remove settling from jet hole, and the time goes up and allows to form settling.
The comparison example II
The oil engine being furnished with 2.2 liters of turbo-supercharger and having electronically controlled fuel injector (1985 Chrysler Le Baron) uses the gasoline of conventional level 87 octane values, unleaded, no washing agent, 2858 miles of drivings on mile journey accumulation ergometer.Repeating to drive by the following cycle: travelled 30 minutes in the urban district, shut down 30 minutes, road running 30 minutes, shut down 30 minutes.It is very poor, representational that motivating force becomes is to shut down unstable, serious weak point to stop backfire and speed shakiness in accelerator.During the hydrocarbon quantity discharged engine idle measured before catalyzed conversion is 804ppm, at 2500 rev/mins of time-division 725ppm.Adopt the pressure differential method also can measure the injector chocking-up degree.In this test, fuel channel is pressurized to 49psig and to injector pulse 0.5 second.Voltage drop value is the rough mensuration degree that injector gets clogged between injector, and promptly maximum and Schwellenwert numerical difference between are big more, and the degree that injector stops up is big more.Be summarized in the table II with travel 2585 miles measurement result of the fuel of no scale remover.
The embodiment I
Abide by top comparison example II, the same fuel charge of automobile, different is that fuel also contains two (2-hydroxyethyl) coconut amines (HECA) of 80ppm.Then automobile being driven with the following cycle: travelled 15 minutes in the urban district, road running 30 minutes, and travelling 15 minutes in the urban district, shut down 2 hours.This test duration accumulation is 308 miles on automobile.After test period finished, motivating force was very good.Under the idling mode before catalyzed conversion, the hydrocarbon quantity discharged is reduced to 65ppm, under 2500 rev/mins, is reduced to 16ppm.Before catalyzed conversion, idling and 2500 rev/mins hydrocarbon quantity discharged and the pressure reduction of various time interval measurements in purifying the driving process are summarized in the table II, and the injector flow reduces measured value and is summarized in the table III.
As seen data from embodiment 1 and table II and table III use the HECA than low concentration that motivating force is significantly improved.Behind quite few mileage that travels, the idle exhaust emission amount reduces significantly, and the flow of the pressure reduction and the injector of flowing through reduces percentage and gets back to " as new " state again.
The table II
Quantity discharged before the catalyzed conversion
Add 2500 rev/mins of △ P of HECA idling and leak PSI
After mile journey HC, CO HC, CO cycle # 1234
ppm % ppm %
0 804 0.68 725 0.31 17 18 20 21
73 813 1.78 188 1.99 17 17 19 22
140 375 0.95 35 1.10 17.5 18.5 19 20.5
219 95 0.70 30 0.75 19 19 19.5 25
308 65 0.67 16 0.69 23 24 24 25
The table III
Cellular type injector flow reduced rate
Add behind the HECA injector numbers 1234
Mile journey of travelling
308 flows reduce % 0001
The comparison example III
Second oil engine (1985 Chrysler Le Baron) of being furnished with 2.2 liters of turbo-supercharger adopts the gasoline of different batches of 87 octane values, unleaded, no scale remover comparison example II and the embodiment I of conventional level, accumulates on the ergometer driving in mile journey.Adopt same drive cycle in the comparison example I.After 4016 miles this oil engine be accredited as stop up and motivating force poor.
Measure the pressure reduction of the preceding quantity discharged of catalyzed conversion and each injector, and be summarized in the table IV with the form of zero mile measurement behind the adding HECA.
The embodiment II
Two (2-hydroxyethyl) coconut amines of about 60ppm are joined in the fuel of comparison example III, and will the automobile of example III be driven with the same cycle of describing in the embodiment I.Measure the pressure reduction of quantity discharged and each injector as described above before the catalyzed conversion.These results are shown in the table IV.Only 357 miles travel after, it is good to be accredited as motivating force.Off-test is pulled down injector and is carried out flow test by aforementioned, and it the results are shown in the table V.
The table IV
Quantity discharged before the catalyzed conversion
Adding 2500 rev/mins of △ P of HECA idling leaks
After mile journey HC, CO HC, CO cycle # 1234
ppm % ppm %
0 148 2.17 126 2.21 11.0 10.0 12.5 10.0
188 190 2.6 125 3.2 15.0 16.0 19.0 21.0
359 112 0.94 53 1.12 15.5 16.0 16.0 16.5
The table V
The flow reduced rate of injector
Add behind the HECA injector numbers 1234
Mile journey of travelling
359 flows reduce % 5210
From table II-V, as seen, just can in the relatively shorter time, reduce the settling of injector tip with the HECA of low concentration.By more as can be known, can not stop the injector tip settling to accumulate faster with traditional vaporizer scale remover.
Data have in the above proved the validity of anti-plugging agent in the gasoline.Simultaneously, this anti-plugging agent for example also has practicality in the diesel oil fuel in other fuel.
Now the anti-plugging agent of describing both can use separately, also can need mix use with demulsifying compound by of the present invention, so that gasoline is separated in any tramp material such as water and the throw out from be present in allocating system.
If water is arranged, its pH value generally is about 7～13.Thereby it is effective that the demulsifying compound that uses with anti-plugging agent is preferably in this pH value scope.Below comparison example and embodiment prove the virtual value of different demulsifying compounds.
The comparison example IV
In this comparison example, test different commercially available demulsifying compounds in 90%(weight) fuel-10%(weight) validity in the system of water.Described fuel contains a kind of binder component, and the latter comprises the following different additive of about 60ppm HECA and 2ppm.Adopt improved multiple contact emulsifying agent test (Multiple Contact Emulsion Test) to measure the validity of different demulsifying compounds.In this test, the water deposit that 10 milliliters of pH values is about after this off-test of 10 joins in the half pint bottle that separates separately.In each bottle, add 100 milliliters of gasoline.Bottle is built, bottle is sidelong on machine mixer, and stirred ten minutes with the speed of about per minute 180 circles.Then bottle is vertically put well, left standstill 1 hour.Then measure mixture, research gasoline layer, water layer and interface with the calibrated scale that provides in the table VI.After mensuration is finished, the petrol level on the interface or on the emulsion layer taken out drop to about 1/4 inch high, and do not destroy interface or water layer.The drain fuel that is drawn into and 100 milliliters new gasoline injected each bottle.Then mixture is stirred and repeat above test, to indicate the several of being seen the poorest grade.Each mixture that the trade mark of the commercially available additive that is adopted, the poorest grade and the several of being tested numbering all provide in the VII below.
The table VI
Be used to observe emulsion test result's standard
The grade emulsive is described
0 no top layer or interface
1 has top layer-not exclusively continuously slightly on the interface
2 thicker top layer-general complete is continuously on the interface
3 the beginning emulsifications, as water layer thick 1/8
4 emulsions such as water layer thick 1/4
5 emulsions such as water layer thick 3/8
6 emulsions such as water layer thick 1/2
7 emulsions such as water layer thick 5/8
8 emulsions such as water layer thick 3/4
9 emulsions such as water layer thick 7/8
10 emulsions are full of water layer fully, the most serious emulsification
The table VII
Emulsion test result
The several numbering that the poorest grade of emulsion breaking title is tested
Tolad T-292 3 2
Tolad T-347 3 2
Tolad T-370 4 1
Nalco 5450 4 1
Nalco 5451 3 4
Nalco 5452 3-4 4
Nalco 5453 4 1
Nalco 85 BD-194 4 1
Nalco 3BD-829 4 1
The embodiment III
100 milliliters of gasoline samples that contain 60ppm HECA are mixed with water deposit after 10 milliliters the comparison example IV off-test.But the demulsifying compound below adopting respectively replaces listing in the demulsifying compound of table VII: Tolad T-500; Tolad T-284; Tolad T-286; Tolad T-326 and Nlalco 5455.Adopt aforesaid through improvement repeat to contact emulsion test, to measure the validity of each sample.These test-results are summarized in the following table VIII.The explanation of every kind of additive is shown in the following table IX.
The table VIII
Emulsion test result
The several numbering that the poorest grade of emulsion breaking title is tested
Tolad T-284 2 4
Tolad T-286 1-2 4
Tolad T-326 2 2
Tolad T-500 2 4
Nalco 5455 2 4
The table IX
The explanation of demulsifying compound
The demulsifying compound explanation
Acidylate polyglycol solution in the Tolad T-284* aromatic hydrocarbon
Alkylaryl sulphonate in Tolad T-286* aromatic hydrocarbon and the Virahol, polyglycol,
Alkyl oxidation of alkyl phenol-formaldehyde resin
O-alkylation alkyl-alkyl phenol-formaldehyde resin in the Tolad T-326* aromatic hydrocarbon oil
Alkyl oxidation of alkyl phenol-formaldehyde resin in Tolad T-500* aromatic hydrocarbon and the alkanol
Alkyl oxidation of alkyl phenol-formaldehyde resin in the Nalco 5455** aromatic solvent
The comparison example V
An oil engine (1985 Chrysler Le Baron) of being furnished with 2.2 liters of turbo-supercharger adopts the unleaded of conventional level 87 octane values, and the fuel of no scale remover drives on mile journey accumulation ergometer.The drive cycle that injector is stopped up is that 30 minutes urban district types travel, and absorbs (shutdown) in 30 minutes, 30 minutes road runnings, absorption (shutdown) in 30 minutes.After 2300 miles, this oil engine is accredited as obstruction.
Measure the pressure reduction of quantity discharged and each injector before the catalyzed conversion, and be shown in the table X with the mensuration form that adds behind the additive zero mile.
The embodiment IV
Present embodiment has shown the validity of the automotive sprayers obstruction that purifies the comparison example V.Method is to adopt a kind of oxide compound blended additive that comprises amine and amine.The fuel that adopts is similar to the comparison example V, but also comprises two (2-hydroxyethyl) coconut amines of 80ppm and two (2-hydroxyethyl) oxidation coconut amines of 10ppm.Drive cycle is same as the embodiment I.Travel after 301 miles, motivating force becomes good from very poor.
Measure the pressure reduction of quantity discharged and each injector as described above before the catalyzed conversion.Its result also is shown in the table X.Injector is pulled down in off-test, and presses preceding method and measure flow, and it the results are shown in the table XI.
According to these results as can be seen, with comprising that amine and amine oxide blended additive have purified the injector that stops up.On other instruction carriage, carry out other test.Have found that under nearly all situation, amine and amine oxide are used, portion all can purify the injector of obstruction in a shorter period.
The table X
Quantity discharged before the catalyzed conversion
Add and add 2500 rev/mins of △ P leakages of idling maximum
Add HC after the agent, CO HC, CO
Mile journey ppm % ppm % cycle # 1234 △ P difference describe
0 491 1.66 175 1.32 14 16 21 19 5 is very poor
151 1,112 2.22 140 2.43 17 19 19 24 7 is very poor
301 128 0.77 61 1.06 18 19 18 19 1 is good
The table XI
Hole injection flow reduced rate
Mile journey injector numbers 1234 that adds additive
301 flows reduce % 2142
The present invention described herein is as gasoline dope, and this binder component can join in the gasoline in any place after the gasoline refining, that is to say to add this additive in refinery or in allocating system.

Claims (10)

1, a kind of motor fuels mixture, it comprises:
A. gasoline
B. anti-plugging agent with following formula:
Figure 87101878_IMG1
Wherein: R 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical substituted alkyl or substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl, aryl, cycloaliphatic radical or heterocyclic radical; And,
C. demulsifying compound, it is selected from
I. acidylate polyglycol
Ii. alkylaryl sulphonate, polyglycol, alkyl oxidation of alkyl phenol-formaldehyde resin;
Iii. alkyl oxidation of alkyl phenol-formaldehyde resin and polyglycol; And,
Iv. alkyl oxidation of alkyl phenol-formaldehyde resin; And their mixture.
2, the fuel composition of claim 1, wherein R 1Be C 6～C 20Alkyl, or alkylated aryl; R 2And R 3Be respectively the C that hydroxyl has replaced 1～C 12Alkyl.
3, a kind of combustion engine fuel multifunctional additive for lubricating oils, described multifunctional additive for lubricating oils comprises:
A. about 5 to about 60%(weight) two (2-hydroxyethyl) coconut amines;
B. about 0.25 to about 10%(weight) a kind of demulsifying compound, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkyl oxidation of alkyl phenol-formaldehyde resin;
ⅲ. alkyl oxidation of alkyl phenol-formaldehyde resin and polyglycol; And,
ⅳ. alkyl oxidation of alkyl phenol-formaldehyde resin; And their mixture; And,
C. about 40 to about 95%(weight) solvent.
4, the fuel of claim 3 adds enriched material and further comprises about 1 to about 15%(weight) two (2-hydroxyethyl) oxidation coconut amines.
5, a kind of combustion engine fuel multifunctional additive for lubricating oils, described multifunctional additive for lubricating oils comprises:
A. about 8 to about 32%(weight) amine;
B. about 2 to about 8%(weight) amine oxide;
C. about 40 to about 95%(weight) solvent; And,
D. about 1 to about 4%(weight) demulsifying compound.
6, a kind ofly reduce and/or prevent the method that porous electric-controlled type fuel injection system in the oil engine is stopped up, this method comprises: a kind of fuel that contains the anti-plugging agent of significant quantity is transported in the described fuel injection system, and described anti-plugging agent is by formula:
Figure 87101878_IMG2
Form.Wherein: R 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl or substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl, aryl, cycloaliphatic radical or heterocyclic radical.
7, the method for claim 6, wherein R 1Be C 6～C 24Alkyl, or alkylated aryl, and R 2And R 3Be respectively the C that hydroxyl has replaced 1～C 12Alkyl.
8, a kind of method that reduces and/or prevent the porous fuel injection system obstruction, this fuel injection system has the transmitter that is placed in the venting port, the suitable ratio of regulating air and fuel, described method comprise fuel are transported in the fuel injection system that this fuel comprises:
A. white gasoline;
B. anti-plugging agent, it is selected from two (2-hydroxyethyl) coconut amines, two (2-hydroxyethyl) Tallow, beef amine, two (2-hydroxyethyl) stearylamide, two (2-hydroxyethyl) rare basic amine of oil and their mixture; And
C. demulsifying compound, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkyl oxidation of alkyl phenol-formaldehyde resin;
ⅲ. alkyl oxidation of alkyl phenol-formaldehyde resin and polyglycol; And,
ⅳ. alkyl oxidation of alkyl phenol-formaldehyde resin; And their mixture.
9, in the method that is used for combustion in IC engine gasoline, gasoline is transported to the combustion zone of oil engine by porous electric-controlled type fuel injection system, and this method improvement comprises a kind of gasoline of burning, and this gasoline contains:
A. the anti-plugging agent of a significant quantity, it is selected from two (2-hydroxyethyl) coconut amines, two (2-hydroxyethyl) Tallow, beef amine, two (2-hydroxyethyl) stearylamide, two (2-hydroxyethyl) oleyl amine and their mixture; And,
B. demulsifying compound, it is selected from:
ⅰ. the acidylate polyglycol;
ⅱ. alkylaryl sulphonate, polyglycol, alkyl oxidation of alkyl phenol-formaldehyde resin;
ⅲ. alkyl oxidation of alkyl phenol-formaldehyde resin and polyglycol; And,
ⅳ. alkyl oxidation of alkyl phenol-formaldehyde resin; And their mixture.
10, a kind of motor fuels mixture, it comprises:
A. gasoline;
B. anti-plugging agent of amine with following formula:
Figure 87101878_IMG3
Wherein: R 1Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl or substituted aryl; R 2And R 3Be respectively C 1～C 24Substituted alkyl, aryl, cycloaliphatic radical or heterocyclic radical; And,
C. anti-plugging agent of amine oxide with following formula structure:
Figure 87101878_IMG4
R wherein 4Be C 6～C 24Alkyl, aryl, cycloaliphatic radical, heterocyclic radical, substituted alkyl, substituted aryl; R 5And R 6Be respectively C 1～C 24Alkyl, aryl, substituted alkyl or aryl, cycloaliphatic radical, heterocyclic radical and their mixture.
CN198787101878A 1986-03-14 1987-03-14 The fuel composition that is used for porous fuel injection system Pending CN87101878A (en)

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CN106635198A (en) * 2016-12-22 2017-05-10 上海灵融实业发展有限公司 Gasoline power improving composite cleansing agent

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CN101046181B (en) * 2006-03-30 2010-05-26 雅富顿公司 Treated port fuel injectors and method for forming film on port type fuel injectors
CN106635198A (en) * 2016-12-22 2017-05-10 上海灵融实业发展有限公司 Gasoline power improving composite cleansing agent

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