CN1637120A - Method for reducing combustion chamber deposit flaking - Google Patents
Method for reducing combustion chamber deposit flaking Download PDFInfo
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- CN1637120A CN1637120A CNA2004100921718A CN200410092171A CN1637120A CN 1637120 A CN1637120 A CN 1637120A CN A2004100921718 A CNA2004100921718 A CN A2004100921718A CN 200410092171 A CN200410092171 A CN 200410092171A CN 1637120 A CN1637120 A CN 1637120A
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- C—CHEMISTRY; METALLURGY
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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
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1828—Salts thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like
- F02M27/02—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like by catalysts
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/12—Inorganic compounds
- C10L1/1275—Inorganic compounds sulfur, tellurium, selenium containing compounds
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1283—Inorganic compounds phosphorus, arsenicum, antimonium containing compounds
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- C10L1/00—Liquid carbonaceous fuels
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L10/00—Use of additives to fuels or fires for particular purposes
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- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
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Abstract
A method reduces combustion chamber deposit flaking and spark ignited internal combustion engines. The method includes supplying a fuel having an additive that includes a metal-containing compound to a spark ignited internal combustion engine. The metal-containing compound is supplied in an amount effective to reduce combustion chamber deposit flaking. In one example, the metal is manganese and the additive compound is MMT. The reduction or elimination of combustion chamber deposit flaking means a reduction in cold start emissions from the engine.
Description
Technical field
Thereby the present invention relates to a kind of method that combustion chamber deposit flaking reduces the cold starting exhaust gas emission that reduces.This method comprises a kind of fuel that contains fuel dope of burning, and this fuel dope contains a kind of metallic compound.An example is that this metallic compound is for containing manganic compound.
Background technology
Spark-ignited internal combustion engine (vaporization, spout fuel injection " PFI ", multi-point injection " MPI ", direct injection gasoline " DIG " etc.) combustion chamber deposit in operation process (CCD) can be accumulated.Generate can not clean-burning macromolecule material for non-complete combustion of fuel, some fuel component generation heat polymerizations in power stroke, and this causes producing settling.This settling layer is created on the cylinder end face and piston tip that is arranged in the combustion chamber.Especially, the settling of piston tip is for fuel and moisture sensitivity, and is wetting and/or just curl easily when being exposed to wet environment and come off by fuel when it.In the cold starting process peeling phenomenon can take place, the settling that combustion flow will come off this moment is blown into exhaust valve seat from the combustion chamber.Thereby the deposit flaking sheet rests on new location, promptly wedge the seal strip of vent valve, obstruction is held fuel/air combustion and is flowed necessary tight seal in pressure stroke, thereby can suppress igniting, therefore for making the engine normal ignition also must prolong the engine start time to remove settling.In this starting process, this combustion flow is disposed in advance in the exhaust system, is catalytic converter input crude fuel, and is not to be that combustion flow is in the cylinder to carry out spark ignition subsequently.Part in this crude fuel is leaked from exhaust after treatment system, and this will cause the discharging of cold starting hydrocarbon " HC ".And when engine was finally lighted a fire, hot burning gas cognition was subsequently lighted this crude fuel.The violent burning meeting of fuel makes the catalytic converter fusing because of the excessive temperature of its generation in exhaust system subsequently, and badly damaged exhaust after treatment system.
After the advanced discharge control method of hydrocarbon discharging occurred when being intended to reduce cold starting, the CCD peeling phenomenon just had been found recently.All these variations be because: find that in the cold starting process with the igniting of floor three-way catalytic converter, the major part in whole vehicle hydrocarbon dischargings produced in its normally used initial 90 seconds.Therefore, shortening this timed interval just becomes very important problem.Governmental environmental protection manager also recognizes this problem; make car manufactures exploitation a kind of with car diagnositc system (OBD) with the monitoring emission control systems; so that this system minimizes to the amount of airborne release hydrocarbon waste gas, and this system can guarantee that it finishes its predict task in the specific warranty period.
The change that emission control is done has caused the cold starting obstacle, this is owing to refuel speed in the cold starting process is higher, cause combustion chamber deposit flaking and wedge the vapor cock seal strip, thereby meeting destroys good sealed state and causes misfiring in compression process.Because of unlit fuel makes hydrocarbon quantity discharged subsequently rise, so this OBD system can detect above-mentioned situation immediately, and lights the trouble indicating lamp (MIL) on the switchboard, needs this moment and please manufacturer carry out correct maintenance.Tend to mainly occur in the engine of higher emissions amount because of CCD peels off the cold starting obstacle that takes place, it has used more multiple cylinder (6,8 and 10 cylinder engines), because these bigger engine start speed are lower, need the longer time that the settling that peels off is blown out from vapor cock.
A kind of solution of peeling off the cold start problem that causes because of CCD is that short-range driving automobile under underload does not carry out soaking thereby this combustion chamber is got time extension.The another kind of method that overcomes this problem is to continue starting blowing away bad deposit flaking layer, during starting, makes the time lengthening 30 seconds that motor speed accelerates, to remove the settling that all the other peel off.But this method can cause the hydrocarbon quantity discharged very high occasionally, also can cause OBD MIL to light.
Summary of the invention
Have been found that the fuel dope that uses the containing metal compound can reduce even eliminate combustion chamber deposit (CCD) and peel off.An example is that a kind of manganic compound MMT that contains can suppress CCD fully and peel off.
A kind of method that reduces combustion chamber deposit flaking in the spark-ignited internal combustion engine that has combustion chamber deposit comprises the steps: to supply with the fuel that comprises a kind of additive to spark-ignited internal combustion engine, this additive comprises a kind of containing metal compound, and wherein the feed rate of containing metal compound should be enough to reduce combustion chamber deposit flaking.
The containing metal compound can be the compound that comprises in the following metal one or more: manganese, platinum, palladium, rhodium, iron, cerium, copper, nickel, silver, cobalt and molybdenum and composition thereof.Describe an example of manganic compound herein in detail, but also can use other containing metallic additive.In each replacement scheme, the metallic compound in the fuel burns in spark-ignited internal combustion engine.Using this containing metallic additive to reduce or to remove CCD peels off.
Adopt fuel described herein and additive in any spark-ignited internal combustion engine, to burn.The specific engines that can be benefited comprise have the vaporizing oil system, the engine of spout fuel injection system, multipoint injection system and direct injection petrol system.The turbocharged type of aforementioned engine and boosting type also can be benefited from it.Other has advanced emission control and comprises as the engine of exhaust gas recirculatioon and also can be benefited.In addition, Otto (otto) circulation and two-stroke internal-combustion engine also can be benefited.
Unleaded or non-plumbous gasoline base in the fuel composition of the present invention is the motor spirit cut of using always, and the general temperature range of the boiling point of this cut is at about 70 °F-440 °F.Above-mentioned gasoline consists essentially of the white gasoline that is applied to spark-ignited internal combustion engine at present of all grades.It generally comprises straight chain and cracking stock simultaneously, contains or do not contain alkylated hydrocarbons, reforming hydrocarbon etc.This gasoline can be prepared into by the same sanitising agent of stable hydrocarbon, antioxidant, dispersion agent, metal passivator, rust-preventive agent, multifunction additive, emulsion splitter, fluidised form carburetion, frostproofer, combustioncatalysts, corrosion inhibitor, emulsifying agent, tensio-active agent, solvent or other similar additives known, and described stable hydrocarbon is straight chain raw material, alkylated product etc. for example.According to estimates under specific circumstances, can add these additives, its concentration should be higher than normal level.
In general, base gasoline is a kind of raw material blend that several refining process is formed that comes from.Final blend also can comprise by other technology such as the made hydrocarbon of alkylation, that is: use an acidic catalyst such as sulfuric acid or hydrofluoric acid and from the aromatic essence of reformer, make C
4Alkene and butane react.
Measure according to standard A STM distillating method (ASTM D-86), be used to prepare the engine gasoline base of fuel blends of the present invention, its initial boiling point at about 70-Yue 100, full boiling point at about 420 °F-Yue 440 °F.Middle gasoline fraction can evaporate in above-mentioned end value scope.
Because sulfur oxide promotes to produce the pungency and the blocking performance of smog and other form atmospheric polluting material easily, so also wish to use the base gasoline of low sulfur content.In the feasible economically scope, the sulphur that exists with common sulfur-containing impurities form in this base gasoline should be and is no more than about 100ppm.Another kind of scheme is to comprise that sulphur content is no more than the fuel of about 30ppm.
The gasoline base that the present invention adopts should be not leaded or be substantially free of lead.But this gasoline can contain other octane promoter of antiknock amount, as cyclopentadienyl nitrosyl nickel, methylphenylamine etc.Also can contain antiknock promotor as 2.4 diacetylmethanes.Under given conditions, wish that also this gasoline contains additional valve and valve seat retreats protective material.Limiting examples comprises: the CaF that boron oxide, bismuth oxide, pottery connect
2, tertiary iron phosphate, Tritolyl Phosphate, phosphorus and sodium based additive etc.This fuel can also comprise antioxidant as 2,6 two-uncles-butylephenol, and 2,6-two-Butylated Hydroxytoluene, phenylenediamine such as N-N '-two sec-butyls-Ursol D, N-isopropyl benzene diamines etc.Simultaneously, this gasoline can also contain dyestuff, metal passivator or other known useful additive.A kind of detailed characteristics of base gasoline commonly used is as follows.Obviously, much other standard and special gasoline also can be used for the applicant's fuel blends.
The characteristic of gasoline
Api gravity (@60F) 50-70
Reid vapor pressure, EPA, (psi) 6-8
Sulphur (ppm) 0-500
Research octane number (RON) 85-120
Motor-method octane number 75-90
R+M/2??????????????????????????????87-110
Oxidisability (%) 0-30
Aromatic series (%) 0-50
Alkene (%) 0-30
Paraffin (%) 30-100
The ASTM distillation
The Vol% vaporization temperature, F
IBP????????????????????????????????70-100
5??????????????????????????????????100-130
10?????????????????????????????????120-140
15?????????????????????????????????140-160
20?????????????????????????????????150-170
30?????????????????????????????????170-190
40?????????????????????????????????190-210
50?????????????????????????????????200-220
60?????????????????????????????????220-240
70?????????????????????????????????240-260
80?????????????????????????????????280-300
90?????????????????????????????????340-370
95?????????????????????????????????380-400
EP?????????????????????????????????420-440
Operable a kind of metal comprises element state and ionic state manganese and precursor thereof, and the mixture that contains manganese metal compound.The described manganic compound that contains can be inorganic or organic.Effectively generate in position equally, the manganese or the mn ion of release or output.
Comprise to the exemplary and indefiniteness of the inorganic metal compound of Shi Yonging in an embodiment as fluorochemical, muriate, bromide, iodide, oxide compound, nitrate, vitriol, phosphoric acid salt, nitride, hydride, oxyhydroxide, carbonate and composition thereof.Metal sulfate and phosphoric acid salt are all very effective, in specific fuel and burn application, the combustion by-products of unwelcome additional sulphur and phosphorus can not occur.Organometallic compound comprises alcohol, aldehyde, ketone, ester, acid anhydride, sulfonate, phosphoric acid salt, inner complex, phenates, crown ether, carboxylic acid, aminocompound, acetyl-pyruvate and composition thereof in an embodiment.
The example that contains the manganese organometallic compound is the tri carbonyl compound of manganese.All provided the instruction about these compounds in many documents, for example United States Patent (USP) 4,568, and 357; 4,674,447; 5,113,803; 5,599,357; 5,944,858 and European patent 466512B1.
The tri carbonyl compound of operable suitable manganese comprises cyclopentadienyl tricarbonyl manganese, methyl cyclopentadienyl tricarbonyl manganese, the dimethyl cyclopentadienyl tricarbonyl manganese, the trimethylammonium cyclopentadienyl tricarbonyl manganese, the tetramethyl-cyclopentadienyl tricarbonyl manganese, the pentamethyl-cyclopentadienyl tricarbonyl manganese, the ethyl cyclopentadienyl tricarbonyl manganese, the diethyl cyclopentadienyl tricarbonyl manganese, the propyl group cyclopentadienyl tricarbonyl manganese, the sec.-propyl cyclopentadienyl tricarbonyl manganese, tertiary butyl cyclopentadienyl tricarbonyl manganese, the octyl group cyclopentadienyl tricarbonyl manganese, the dodecyl cyclopentadienyl tricarbonyl manganese, the ethyl-methyl cyclopentadienyl tricarbonyl manganese, indenyl manganese tricarbonyls etc. comprise in the above-claimed cpd two or more mixture.A kind of alternative method is to use and is liquid cyclopentadienyl tricarbonyl manganese under the room temperature, as methyl cyclopentadienyl tricarbonyl manganese, ethyl cyclopentadienyl tricarbonyl manganese, the liquid form mixt of cyclopentadienyl tricarbonyl manganese and methyl cyclopentadienyl tricarbonyl manganese, the mixture of methyl cyclopentadienyl tricarbonyl manganese and ethyl cyclopentadienyl tricarbonyl manganese, or the like.
The preparation method of above-claimed cpd is on the books in the literature, as United States Patent (USP) 2818417, quotes in full its content at this.
When the used additive of preparation method described herein, the CCD that the consumption of this containing metal compound must be enough to reduce or eliminate in the spark-ignited internal combustion engine peels off.According to the mixture of specific metal or metal mixture, containing metal compound, this consumption can be different.Contain in the example of manganic compound, the add-on of manganese can be every liter of about 50mg manganese of about 1-.
The containing metal compound is considered to serve as free radical absorption agent and combustioncatalysts.As the free radical absorption agent, this compound can stop free radical stimulate fuel polymerization reaction take place, thereby by the influence of this approach restriction to hydrocarbonaceous CCD.As combustioncatalysts, for example manganese can participate in removing the process of CCD by promoting the oxidation of carbon at a lower temperature with the catalysis form.
Term " cold start emission " refers to and is consistent with its industrial definition.The industry recognized definition of cold start emission can be referring to FTP-75 (federal test method).The detailed content of this test method is recorded in federal codes and standards (Code of Federal Regulations) (CFR40, the 86th part).Briefly, this test method comprises following three stages: 1) cold starting, 2) transient state and 3) hot start.The FTP-75 discharge cycle has been simulated V-bar with 21.2mph (34.1km/h) travel 11.04 miles (17.77km) in 1874 seconds time.Before test, vehicle be adjusted in all night 25+/-5C to be to guarantee cold start conditions.After cold starting begins, next be transient phases.Vehicle stops subsequently, keeps 10 minutes soaking before the hot stage is carried out in starting once more.The ejecta in each stage is collected in the independent teflon bag that is used for each test phase respectively, analyzes subsequently.Every kind of composition (HC, CO, CO in the ejecta in each stage
2, NOx etc.) amount with the g/ mile (g/km) expression.For hydrocarbon ejecta (HC), cold-start phase is the most important, because its quantity discharged has accounted for the 80-90% of three phases total amount.
Embodiment
In Engine Block Test, to comprising and not comprising that the fuel of containing metal compound compares.To contain manganese MMT as additive, its usage ratio is every liter of fuel 8.25mg manganese.
The vehicle that is used for this test is the Dodge Intrepid of six cylinder engine.Under the situation of using the gasoline that does not add CITGO RUL, travel 3000 miles in this test period.During end of test (EOT), engine stripping is got off, according to the method for Gautam T.Kalghatgi in SAE collection of thesis 2002-01-2833, assessment CCD peels off situation.
Testing method: the CCD that Dodge Intrepid is done peels off test
Ethyl test summary:
Vehicle: Chrysler Dodge Intrepid
Fuel: the CITGO routine is unleaded
Test #1: do not use the MMT additive
Test #2: use the MMT additive
Cycle: IVD Chassis Dyno cycle (average 45mph)
Two classes of every days (about 600 miles)
Soaking all night
Accumulative total 3000 miles per hours finish test;
When end of test (EOT):
1 by each conventional IVD/CCD test dismounting engine
2 usefulness floating rules are measured the thickness of deposits at top and piston place
3 usefulness family expenses plant water-jets spray suds (containing 1 dropping liquid attitude household detergent in every 100mL water) to piston tip
After 43 hours, piston tip is taken pictures, mark the degree of peeling off
5 spritzpistole tops once more, placement is spent the night
6 pairs of piston tip are taken pictures, and mark the degree of peeling off
The settling that 7 vacuum removings peel off, and weigh
8 pairs of piston tip are taken pictures
9 usefulness floating rules are measured the thickness of relict sediment
10 strike off all settlings of piston tip
Thorough IVD and CCD mensuration are carried out in 11 pairs of tops.
Six valves of term " on average " expression or six piston tip or six cylinder head are corresponding to the average deposition amount of six position of piston.
Table 1: contain manganese additive and suppress the situation that CCD peels off
Add | The amount of peeling off of CCD (milligram) | Engine CCD total amount (milligram) | Engine IVD (milligram) |
Not | ????89.4 | ????783.4 | ????312.2 |
Be | ????0 | ????688.9 | ????305.9 |
From this test examples obviously as can be seen, use specific containing metallic additive described herein to remove combustion chamber deposit flaking fully.In other words, used this additive not have CCD to peel off.Also can use other containing metallic additive, its usage ratio can be different.Change additive or change its usage ratio, just can control the reduction of peeling off.It is believed that when employing contains manganese additive usage ratio is that the CCD that every liter of about 2mg manganese of fuel will reduce up to 50% peels off.
Owing to find that not producing CCD peels off, can obtain obviously burning more completely, particularly during the cold starting of engine operation.Do not produce peeling off of sealing place of stopping up vent valve.Therefore, have only the crude fuel of less amount to enter exhaust system by cylinder.Therefore, in having the spark-ignited internal combustion engine of combustion chamber deposit, use this additive can reduce the hydrocarbon that discharges in the cold starting.
Be to be understood that, reagent and the composition that any place mentions by chemical name in this specification sheets or the claim, no matter be odd number or plural form, all refer to their materials before contacting with other material of mentioning with chemical name or chemical type (as basic fuel, solvent etc.) form.No matter in the mixture of gained or solution or reaction medium which kind of chemical transformation, transformation and/or reaction (if generation) take place, these change, change and/or reaction is the natural result that uses this particular agent and/or composition under condition of the present invention.Therefore this reagent and composition refer to expecting chemical reaction (as forming organometallic compound) or formation contemplated composition (as multifunctional additive for lubricating oils or adduction fuel blends) blended component.What also will know is that this binder component also can itself add respectively or be mixed in the basic fuel or with it and mixes, and/or can be used as the component that is used to form effective compositions of additives and/or sub-combinations thereof thing.Therefore, even claim hereinafter may be mentioned material, component and/or composition with present tense (" comprising ", "Yes" etc.), but this term refers to above-mentioned substance, component or composition before being in harmonious proportion with one or more other materials of the present invention, component and/or composition for the first time or mixing.In the process of this mediation or married operation or its immediately, this material, component or composition may be lost its intrinsic person's character because of chemical reaction or transformation take place, and this point is for accurate understanding with understand this specification sheets and claim is unessential fully.
A series of United States Patent (USP)s, disclosed foreign patent application and disclosed technical article have all been quoted in many places in this manual.All these documents of quoting are all clear and definite in this article and intactly be included in the present specification as entire teachings.
The present invention is easy to make a large amount of changes in force.Therefore aforementioned content and do not mean that, also should not be construed as and limit the present invention in the aforesaid specific embodiment.On the contrary, protection domain be by hereinafter claim and quite content limited as Legal Papers.
The patentee does not really want any disclosed embodiment is contributed to the public, and the scope of any disclosed improvement or change may be on the literal not in the scope in this claim, but they are still the part of purport of the present invention.
Claims (2)
1. a minimizing has the method for combustion chamber deposit flaking in the spark-ignited internal combustion engine of combustion chamber deposit, comprises the steps:
Supply with the fuel that comprises additive to spark-ignited internal combustion engine, described additive comprises the containing metal compound,
Wherein the feed rate of containing metal compound can effectively reduce combustion chamber deposit flaking.
2. a minimizing has the method for the spark-ignited internal combustion engine cold start emission of combustion chamber deposit, comprises the steps:
Supply with the fuel that comprises additive to spark-ignited internal combustion engine, described additive comprises the containing metal compound,
Wherein the feed rate of containing metal compound can effectively reduce cold start emission.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/696618 | 2003-10-29 | ||
US10/696,618 US20050091913A1 (en) | 2003-10-29 | 2003-10-29 | Method for reducing combustion chamber deposit flaking |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN2010102753375A Division CN101914397A (en) | 2003-10-29 | 2004-10-28 | Reduce the method for combustion chamber deposit flaking |
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CN1637120A true CN1637120A (en) | 2005-07-13 |
Family
ID=34423374
Family Applications (2)
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CNA2004100921718A Pending CN1637120A (en) | 2003-10-29 | 2004-10-28 | Method for reducing combustion chamber deposit flaking |
CN2010102753375A Pending CN101914397A (en) | 2003-10-29 | 2004-10-28 | Reduce the method for combustion chamber deposit flaking |
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Application Number | Title | Priority Date | Filing Date |
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CN2010102753375A Pending CN101914397A (en) | 2003-10-29 | 2004-10-28 | Reduce the method for combustion chamber deposit flaking |
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US (1) | US20050091913A1 (en) |
EP (1) | EP1528097B1 (en) |
JP (1) | JP2005133720A (en) |
KR (1) | KR20050040783A (en) |
CN (2) | CN1637120A (en) |
AR (1) | AR046559A1 (en) |
AT (1) | ATE491012T1 (en) |
AU (1) | AU2004218620A1 (en) |
BR (1) | BRPI0404762A (en) |
CA (2) | CA2482735C (en) |
DE (1) | DE602004030408D1 (en) |
MX (1) | MXPA04010020A (en) |
RU (1) | RU2283437C2 (en) |
SG (1) | SG111280A1 (en) |
ZA (1) | ZA200408543B (en) |
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CN103965978A (en) * | 2014-05-09 | 2014-08-06 | 陕西禾合化工科技有限公司 | Transition metal gasoline antiknock agent |
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-
2003
- 2003-10-29 US US10/696,618 patent/US20050091913A1/en not_active Abandoned
-
2004
- 2004-09-28 CA CA002482735A patent/CA2482735C/en not_active Expired - Lifetime
- 2004-09-28 CA CA2677761A patent/CA2677761C/en not_active Expired - Lifetime
- 2004-10-05 AU AU2004218620A patent/AU2004218620A1/en not_active Abandoned
- 2004-10-12 MX MXPA04010020A patent/MXPA04010020A/en active IP Right Grant
- 2004-10-19 DE DE602004030408T patent/DE602004030408D1/en active Active
- 2004-10-19 EP EP04024823A patent/EP1528097B1/en not_active Not-in-force
- 2004-10-19 AT AT04024823T patent/ATE491012T1/en not_active IP Right Cessation
- 2004-10-21 ZA ZA2004/08543A patent/ZA200408543B/en unknown
- 2004-10-25 JP JP2004309792A patent/JP2005133720A/en active Pending
- 2004-10-26 AR ARP040103895A patent/AR046559A1/en active IP Right Grant
- 2004-10-28 KR KR1020040086425A patent/KR20050040783A/en active Search and Examination
- 2004-10-28 CN CNA2004100921718A patent/CN1637120A/en active Pending
- 2004-10-28 SG SG200406302A patent/SG111280A1/en unknown
- 2004-10-28 CN CN2010102753375A patent/CN101914397A/en active Pending
- 2004-10-28 RU RU2004131494/06A patent/RU2283437C2/en not_active IP Right Cessation
- 2004-10-28 BR BR0404762-1A patent/BRPI0404762A/en not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101343578B (en) * | 2007-07-10 | 2012-06-13 | 雅富顿公司 | Fuel composition comprising a nitrogen-containing compound |
CN103965978A (en) * | 2014-05-09 | 2014-08-06 | 陕西禾合化工科技有限公司 | Transition metal gasoline antiknock agent |
Also Published As
Publication number | Publication date |
---|---|
EP1528097A2 (en) | 2005-05-04 |
EP1528097A3 (en) | 2005-07-13 |
ZA200408543B (en) | 2005-09-28 |
BRPI0404762A (en) | 2005-06-28 |
MXPA04010020A (en) | 2005-05-03 |
ATE491012T1 (en) | 2010-12-15 |
RU2004131494A (en) | 2006-05-10 |
CA2482735A1 (en) | 2005-04-29 |
AU2004218620A1 (en) | 2005-05-19 |
DE602004030408D1 (en) | 2011-01-20 |
KR20050040783A (en) | 2005-05-03 |
US20050091913A1 (en) | 2005-05-05 |
RU2283437C2 (en) | 2006-09-10 |
SG111280A1 (en) | 2005-05-30 |
CN101914397A (en) | 2010-12-15 |
CA2482735C (en) | 2009-11-24 |
JP2005133720A (en) | 2005-05-26 |
CA2677761C (en) | 2011-09-13 |
CA2677761A1 (en) | 2005-04-29 |
EP1528097B1 (en) | 2010-12-08 |
AR046559A1 (en) | 2005-12-14 |
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