CN100350024C - Fuel additive - Google Patents

Fuel additive Download PDF

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Publication number
CN100350024C
CN100350024C CNB018084966A CN01808496A CN100350024C CN 100350024 C CN100350024 C CN 100350024C CN B018084966 A CNB018084966 A CN B018084966A CN 01808496 A CN01808496 A CN 01808496A CN 100350024 C CN100350024 C CN 100350024C
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China
Prior art keywords
fuel
composition
additive composition
alcohol
acid
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Expired - Fee Related
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CNB018084966A
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Chinese (zh)
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CN1681908A (en
Inventor
A·雷
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O2Diesel Europe Ltd
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AAE Technologies International PLC
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Priority claimed from GB0004522A external-priority patent/GB0004522D0/en
Priority claimed from GB0004519A external-priority patent/GB0004519D0/en
Application filed by AAE Technologies International PLC filed Critical AAE Technologies International PLC
Publication of CN1681908A publication Critical patent/CN1681908A/en
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Publication of CN100350024C publication Critical patent/CN100350024C/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/192—Macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

There is described a fuel additive composition comprising an alkanolamide, an alkoxylated alcohol, an alkoxylated fatty acid, or a derivative thereof, in which the degree of alkoxylation of the C18 to C22 fatty acid is from 0.5 to 5 mols of alkoxylate to 1 mol of fatty acid. There is also described a fuel composition comprising a liquid hydrocarbon fuel and a surfactant composition according to the invention. A method of running an internal combustion engine comprising the use of such a fuel is also described.

Description

Fuel dope
The present invention relates to comprise the preparation method of fresh fuel composition and the described fuel composition and the tensio-active agent of new surfactant composition.
International Patent Application WO 98/17745 has been described the surfactant composition that comprises following component:
The 25%v/v diglycollic amide,
The 50%v/v ethoxylated alcohol and
25%v/v is with 14 chain fatty acids of seven ethoxylation groups.
WO ' 745 has particularly described the fuel composition that especially comprises the additive of being made by the ethoxylate of fatty diglycollic amide, alcohol ethoxylate and lipid acid, wherein ethoxylation degree is selected, so that formed fuel composition steady in a long-term.
Specifically, WO ' 745 has instructed the purposes of lauric acid and bay diglycollic amide.
Common unsettled International Patent Application WO 99/20715 (authorizing Pure Energy Corporation) has been described similar surfactant composition, and wherein the hydrocarbon chain length of used lipid acid is C 9-C 15
In addition, US6,017,369 to have described a kind of diesel oil, ethanol and carbon chain lengths of especially comprising be C 9-C 15The diesel fuel composition of lipid acid.
Although described additive has obviously reduced discharge and can use by lower concentration, they still have following shortcoming: for example, lauric acid has 44-46 ℃ relative high-melting-point.Therefore, in room temperature, lauric acid is the wax shape and is difficult to preparation.
Surprisingly, we have found to overcome or alleviate the new surface active agents fuel dope of known prior art compositions problem.
According to the present invention, we provide a kind of fuel additive composition, and it comprises alkanolamide, the pure and mild alkoxylate C of alkoxylate 18-C 22The lipid acid or derivatives thereof, wherein, the degree of alkoxylation of lipid acid from 0.5 to 5 mole of alkoxy thing/1 mole of oleic acid.
Preferably, described alkanolamide is a glycollic amide, more preferably diglycollic amide.Especially preferred is diglycollic amide, particularly super (super) diglycollic amide.The super diglycollic amide of term means such diglycollic amide, and wherein nitrogen-atoms is replaced by alkyl substituent, and described alkyl substituent for example is: C 5-C 20, preferred C 8-C 18, more preferably C 10-C 18Alkyl substituent.Most preferred diglycollic amide has C 18Alkyl substituent, i.e. oil base diglycollic amide.
Three kinds of industrial approach that obtain alkanolamide are arranged;
Acid+alkanolamine=alkanolamide+water
Vegetables oil or animal oil (triglyceride level)+alkanolamine=alkanolamide+glycerol
Methyl esters+alkanolamine=alkanolamide+methyl alcohol
These approach are listed by the product quality that increases.Approach via acid usually uses excessive alkanolamine, compares the higher product of amide content to produce with the sour resulting product that uses stoichiometric ratio; These products are referred to as the Kritchevsky acid amides sometimes.The product that is obtained by the reaction of alkanolamide that is essentially stoichiometric ratio and fatty acid ester is called super acid amides; Described fatty acid ester is methyl esters or glyceryl ester typically.
Alcohol alcoxylates is ethoxylated alcohol preferably.Importantly, described ethoxylated alcohol is an oil soluble alcohol.Therefore, alkanol be preferred and they can be primary, the second month in a season or tertiary alkanol, especially primary alkanol.Because the oily solubleness of alcohol can change with the length of ethoxylated alcohol carbochain, therefore, alkanol is C preferably 5-C 22Alkanol, more preferably C 5-C 15Alkanol.Ethoxylated alcohol can comprise the mixture of alkanol.Yet preferably, in described mixture, a kind of alkanol is occupied an leading position.So most preferred alkanol mainly is C 9-C 11Alkanol.In addition, the ethoxylation degree of alcohol can change, and oily solubleness will reduce with the increase of ethoxylation degree usually.Preferably, the ratio of ethoxylate and alcohol is greater than 2.More preferably, the ratio of ethoxylate and alcohol is between 1 and 10, preferably between 1 and 5, more preferably between 1 and 3, especially between 2 and 3.Industrial available ethoxylated alcohol is especially preferred, and wherein said ethoxylate is 2.75 with the ratio of alcohol.Such alcohol ethoxylate obtains with NEODOL91/2.5.
Fatty acid ethoxylate can comprise the mixture of free acid, ester, ester or the mixture of acid and one or more esters.When using fatty acid ester ethoxylate, preferably, described ester is the oleic acid alkyl ester, preferably oleic acid C 1-C 10Alkyl ester, as ethyl oleate, Witconol 2301 especially.Derivative of fatty acid preferably can comprise the ester of any known ester moiety traditionally, yet preferably, described ester is an alkyl ester.Alkyl can be primary, the second month in a season or tertiary alkyl.Yet preferred ester group is a straight chained alkyl, and alkyl chain length is C 1-C 10Especially preferred is methyl esters.
Fatty acid group can be any known C 18-C 22Lipid acid, but oleic acid (C preferably 18).
The alkyl ester fatty acid ethoxylate can the known ordinary method of utilization itself prepare.Yet present technology only allows to make fatty acid ester carry out ethoxylation by PEG/ lipid acid approach, wherein at general formula R COOR 1Lipid acid in, R 1Be methyl.
Have found that described ethoxylated fatty acid ester can be by lipid acid and methoxy poly (ethylene glycol) (PEG) or any other alcohol ethoxylate such as C 9Or C 11The esterification of alcohol ethoxylate and preparing.
Described new method can be produced the ethoxylated fatty acid ester of following general formula:
RCO[CH 2CH 2O] nOR 1
R is C in the formula 8-C 20Alkyl;
R 1Be C 1-C 10Alkyl; And n is the integer of 1-10.
In addition, the ethoxylated fatty acid of formula I can be by RCOOH and R 1[CH 2CH 2O] nThe esterification of OH and prepare R, R in the formula 1As above define with n.
Yet alcohol ethoxylate can be an alkyl phenol ethoxylate for example.
Degree to alkoxylate (for example ethoxylation, propoxylation or its mixing) is selected, so that performance the best of the blending of the tensio-active agent of feasible and other two kinds of selections, and described degree of alkoxylation can be 0.5-5, and more preferably 0.5-2.5.Especially preferred is that oxyalkylation comprises oxyethylation.Product suitable in this scope for example can be obtained by the addition reaction of 1 moles of ethylene oxide and 1 mole of oleic acid or derivatives thereof.
Fatty acid ethoxylate, for example the oleic acid ethoxylate can be derived by the plurality of raw materials that is easy to extensively to obtain and obtained.Yet, in the preferred embodiment of the invention, can produce fatty acid ethoxylate by the ethoxylation or the esterification of acid, for example tallow or vegetables oil such as soybean etc. derive and obtain by animal tallow in described acid.
Therefore, the oleic acid precursor mainly can be lipid acid such as the oleic acid of for example 65-70%v/v, but also can comprise linolic acid, 10-12%v/v for example, and can comprise a spot of stearic acid, palmitinic acid and/or Pork and beans acid.
The fatty acid alkoxylates for example ratio of oleic acid alcoxylates and alkanolamide can change slightly, but preferably 1: 1v/v.
Additive of the present invention can be added in any known hydrocarbon fuel, and for example diesel oil, gasoline or alcohol are as in the ethanol, and described fuel can be moisture or not moisture.As if in the time of in being added into based on the fuel of low distillate, the present invention has good especially effect.
Preferred additives of the present invention is nonionogenic tenside and surfactant mixtures preferably.Preferable feature of the present invention is: character and concentration by dissolved additive in fuel (and existing water or other non-fuel liquid) are come the option table surface-active agent.For this reason, can consider the hydrophile-lyophile balance (HLB) of tensio-active agent easily, this value is calculated by following formula.
The total molal weight in the molal weight of HLB=hydrophilic chain * 20/
This value will depend on hydrophilic chain, the length of ethoxylation chain normally.Because bigger dissolving power, therefore the length of described chain will increase solubleness.
As the composition of describing in WO98/17745, surfactant mixtures is preferred, preferably selects and the fuel corresponding mixture.
The present invention has the ability that the HLB of unified any liquid fuel requires, and this makes that again a kind of dosage that uses in the fuel can be more than the C5 carbochain.Its benefit is: the direct treatment capacity relevant with helping solvency power.
Preferably, oleic ethoxylate has been formed the about 25% of additive volume, and more preferably, alcohol ethoxylate comprises 50% of additive volume.
Additive of the present invention can be added in the hydrocarbon fuel, for example diesel oil, gasoline or alcohol is as in the ethanol, the described fuel water water that maybe can undope that can mix.In addition, hydrocarbon fuel can be petroleum based fuels such as diesel oil or gasoline and pure as the alcoholic acid mixture.As if in the time of in being added into based on the synthol of low distillate, the present invention has good especially effect.
Hydrocarbon fuel can comprise any known hydrocarbon fuel or its mixture, and therefore, described fuel is including, but not limited to diesel oil, for example petroleum diesel, gasoline, aviation fuel, alcohol etc.
In an embodiment of fuel composition of the present invention, hydrocarbon fuel is a petroleum diesel fuel.Described fuel can be obtained by the distillation of oil usually, and its efficient can be measured by cetane value.The suitable diesel oil fuel that uses for the present invention has the cetane value of 35-60, preferred 40-50 usually.Mix the diesel oil amount that forms fuel composition of the present invention and count 60%v/v-95%v/v with the cumulative volume of fuel consumption.
Another feature of the present invention is that hydrocarbon fuel such as diesel oil or gasoline can contain a certain amount of oxygenating agents, for example pure, alkanol, for example ethanol.When having alcohol, its amount especially changes the character of based on fuel, but its amount can be 1-50%v/v, preferred 5-20% v/v.
With regard to fuel, ethanol can be produced by the fermentation of generation of mineral fuel raw material or the sugar that obtains by being derived by cereal or other biomaterial.Therefore, the ethanol that is suitable for for fuel composition use of the present invention can be the fuel-grade ethanol of being derived and being obtained by the fermentation using bacteria of yeast or starch base sugar.Described starch base sugar can be extracted by corn, sugarcane, tapioca (flour) and beet.In addition, fuel-grade ethanol can be by the protease hydrolysate production of known diluted acid and/or concentrated acid and/or particular organisms material, for example, produce by the Mierocrystalline cellulose part that comprises municipal solid waste, waste paper, paper mill sludge, the such industrial waste of sawdust.Biomaterial also can be from agriculture residue, for example comprise in meter shell and the paper mill mud and collecting.
The suitable fuel-grade ethanol of using for the present invention can be not moisture or the water of impure amount only.In addition, the suitable fuel-grade ethanol of using for the present invention can contain the water (aqueous ethanol) up to the more a large amount of 5%w/w.
In the past, ethanol is used in combination with diesel oil fuel and will goes wrong, wherein ethanol/diesel oil fuel mixture will undesirably be divided into two different phases, when especially having water, and will make the mixture that obtains be not suitable for use in ignitable fuel.Utilize fuel dope of the present invention, make aqueous ethanol to carry out gratifying the mixing, and can not form two phases with conventional diesel oil fuel.The fuel-grade ethanol of utilization blending according to the present invention will be given the combustioncharacteristics of whole fuel composition with hope; As the fuel stability that improves, smog still less and particulate matter, lower CO and NO xDischarging, the knock characteristic of improvement, and/or the antifreeze characteristic of improving.
On the other hand, the invention provides a kind of fuel composition that comprises light ends and aforementioned surfactants fuel dope.
The existence of additive of the present invention, to guarantee that fuel composition forms the uniform composition of all-the-time stable and produces individual layer simultaneously, this will cause burning better more completely, and this will reduce pollution again and increase the mileage that per gallon gasoline can travel.
Therefore, propellant combination, particularly alcohol-group fuel can burn more accurately at colder when filling with substance, so that reduce the ironic formiate will make engine aging usually, to exist owing to aldehyde peracid and peroxide reactions.
Therefore, we also provide the fuel composition that comprises previously described fuel and additive for hydrocarbon fuel.
In described fuel composition, the concentration of additive can be very low, is generally 0.5-50: 1000v/v, and preferred about 1: 1000-30: 1000v/v, and most preferably be 1-3: 100v/v.When being dosage but not performance,, add more additive on technology or when preferential economically as if all without any benefit unless need the dual function of solubility promoter.Yet, the ratio of additive and fuel especially based on fuel character and change.Therefore, for example, when fuel was aqueous ethanol/diesel fuel mixtures, the ratio of additive and fuel can be up to 5%v/v, for example 0.1-5%v/v, more preferably 1-3%v/v.In addition, when fuel was dehydrated alcohol/diesel fuel mixtures, the ratio of additive and fuel can be up to 3%v/v, for example 0.1-3%v/v.The amount of alcohol that is present in the diesel mixture of the present invention can be 5-25%v/v, preferred 7-10%v/v, especially 7.7%v/v.When the ethanol in the mixture was aqueous ethanol, the existing water yield can be 4-6%v/v in ethanol percentage ratio.
In addition, when fuel was gasoline or gasoline/alcohol mixture, the ratio of additive and fuel can be up to 5%v/v, as 0.1-5%v/v, preferably up to 3%v/v, for example 0.1-3%v/v, more preferably from 1-3%v/v.The amount of alcohol that is present in gasoline/alcohol mixture of the present invention is 1-25%v/v, preferred 5-25%v/v, more preferably 7-10%v/v, especially 7.7%v/v.When fuel was aqueous ethanol/gasoline mixture, the ratio of additive and fuel can be up to 5% v/v.In addition, when fuel was dehydrated alcohol/gasoline mixture, the ratio of additive and fuel can be up to 3%v/v.
Exist additive of the present invention will guarantee that fuel composition forms the uniform composition of all-the-time stable and produces individual layer simultaneously, such result will cause burning better more completely, and this will reduce pollution and increase the mileage that per gallon gasoline can travel.
Therefore, the fuel of blending, particularly alcohol-group fuel utilize colder when filling with substance to burn more accurately, thereby reduce the ironic formiate will make engine aging usually, to be existed by aldehyde peracid and peroxide reactions.
In addition, we also provide the working method to engine, and described engine is fit to use alkyl or alcohol-group fuel, and described fuel comprises the foregoing fuel composition of use.
It will be particularly advantageous using the fuel additive composition that comprises oleic acid ethoxylate or derivatives thereof with above-mentioned diesel fuel composition, especially diesel oil/alcohol composition.Therefore, according to another characteristic of the invention, we provide the fuel composition that comprises diesel oil fuel, pure and mild foregoing surfactant additive.
Alcohol is ethanol preferably.Randomly, Dresel fuel compositions of the present invention can also additionally comprise for example C of the oleic alkyl ester of use 1-C 6Alkyl alcohol or long chain aliphatic alcohol, and optional alkyl alcohol C for example 3-C 6The solubility promoter of alcohol.
According to another characteristic of the invention, we provide and used the oleic acid or derivatives thereof when preparing as previously mentioned surfactant additive.
According to another characteristic of the invention, we provide and used the oleic acid or derivatives thereof when the foregoing fuel compositions of preparation.
Now, only will the present invention be described by embodiment.
Embodiment 1
Emission test
Carry out emission test at the fuel composition that comprises 95% diesel oil, 5% alcohol mixture and AAE01.
AAE01 contains 25%v/v oleic acid diethyl amide, 50%v/v NEODOL 91/2.5 and the oleic surfactant composition of 25%v/v, wherein contains the ethoxylation group of a molar equivalent.
1.1 test engine
The general feature of test engine is listed in the table 1.
The general feature of table 1. test engine
Make model VOLVO DH10A-285
Number of cylinders and layout (lay-out) 6, straight line
Free air delivery 9.6 cubic decimeter
Injection pump The online pump of electric-controlled mechanical
Peak power output 2000 liters/timesharing 210kW
Peak torque 1450 liters/timesharing 1200Nm
Compression ratio 20∶1
Firing system Direct injection, turbo-charging, in cold
Quantity discharged Europe II
1.2 testing apparatus and step
The all devices that is used for measuring regulated emissions (Co, HC, Nox and particulate matter) is consistent with the specification of the measurement system that ECE regulation No.49/02 annex 4 provides.
The hydrodynamometer of Zollner and " PUMA Test Assistant " hierarchy of control of AVL are used for handling and controlling the engine of test.Utilize the analytical system of BOO Instrument AB to measure the gaseous emissions of regulation.Particulate matter is collected with AVL Mini Dilution Tunnel 474.Used particulate filter is a Pallflex TXH120WW φ 70mm strainer.
Test procedure is the test according to 13 kinds of modes of ECE regulation No.49/02.The peak power output that utilizes each fuel to obtain is used for determining the load setting of dynamometer.
Test is carried out under normal probe temperature.
FTIR measures, from the formaldehyde of heavy duty engine
In the heavy duty engine test, utilize Fourier transform infrared (FTIR) system (SESAM II Fast is made by Siemens AG (FRG)) to measure many unspecified compounds, comprise formaldehyde.Utilize this system, can be with the time interval measurement in a second discharging composition more than 20 kinds.
1.3 test result
Utilize peak power that D1 fuel obtains in the time of 2000 rev/mins for 210kW and 1450 rev/mins the time peak torque be 1200Nm.When comparing, utilize the power loss of fuel D2 to be lower than 1% with D1 fuel.When comparing, utilize the power loss of fuel D3 and D4 to be respectively 5% and 7% with D1 fuel.
Test according to the ECE R49 13-mode that is used for heavy test, emission test the results are shown in following table 2.And utilize the test of each fuel.
When comparing, observed the increase of the HC quantity discharged of fuel D3 and D4 with fuel D1.
Utilize fuel D2, D3 and D4, its NO xAs if quantity discharged want Billy low slightly with D1 fuel.Yet because the uncertainty of measuring method, therefore being lower than 5% change can not think clearly.
Utilize D2 fuel, its granular material discharged Billy's usefulness D1 fuel low about 11% of wanting.Utilize D3 and D4 fuel, its granular material discharged Billy's usefulness D1 fuel low 20% and 27% of wanting respectively.As if in addition, compare with D1 fuel, the black smoke (Bosch cigarette) that utilizes fuel D2, D3 and D4 to be produced is lower.
Table 2. utilizes VOVLO DH10A-285 engine, according to the quantity discharged test result of ECE R49 test procedure
Fuel CO (g/kWh) HC (g/kWh) NO x(g/kWh) Particulate matter (g/kWh) CO 2(g/kWh) Fuel concentration (g/kWh) Bosch cigarette *
D1 (base-material) 0.51 0.15 6.3 0.105 688 230 0.50
D2 (base-material+2% AAE01) 0.51 0.15 6.2 0.093 693 231 0.48
D3 (base-material+2% AAE01+2%H20) 0.51 0.20 6.1 0.084 696 233 0.41
D4 (base-material+1% AAE01+5%MTBE) 0.51 0.20 6.0 0.076 698 235 0.40
* the mean value that does not have gravity factor
The FTIR measuring result is listed in the table 3.The most compositions that record in the waste gas by the discharge of VOLVO DH10A-285 engine are lower than the limit of detection of FTIR equipment.As if utilize the formaldehyde emission of D3 fuel to want the formaldehyde emission of a little higher than D2 fuel.Difference is caused by high capacity mode 6 and 8.Utilize the octane quantity discharged of D3 fuel to be higher than the octane quantity discharged of utilizing D2 fuel, this result with the regulated emissions that is shown in Table 2 is consistent.
Table 3. utilizes VOLVO DH10A-285 engine, by the FTIR measuring result of ECE R49 test
Fuel N 2O (mg/kWh) NH 3 (mg/kWh) CH 2O (mg/kWh) CH 4 (mg/kWh) BNZ (mg/kWh) NC 8 (mg/kWh)
D2 bd bd 24 bd bd 97
D3 bd bd 35 BD BD 120
Bd=is lower than limit of detection
Embodiment 2
The light duty engine emission test
2.1 testing vehicle
The general feature of the fuel combustion vehicle that uses in the discharge test is listed in the table 4.
The general feature of table 4. testing vehicle
Make model Ford Mondeo，1.6BFP/270
Model year 1998
The odometer reading 29100km
Variator Manually, 5
Number of cylinders and layout 4
Free air delivery 1.6dm 3
Peak power output 66kW
The absolute quantity discharged of utilizing FTIR equipment to obtain can obviously be different from the quantity discharged of utilizing conventional measurement techniques to obtain.Yet the FTIR technology can be used for the result of comparison different fuel.Because therefore the low-down hydrocarbon quantity discharged of diesel motor, can utilize most compounds of FTIR device measuring all to be lower than limit of detection.When considering diesel motor, FTIR is suitable for monitoring formaldehyde emissions most.The example of the compound of record is as follows during measuring:
Formaldehyde (CH 2O)
Nitrogen peroxide (NO 2)
Nitrous oxide (N 2O)
Ammonium (NH 3)
Methane (CH 4)
Acetylene (C 2H 2)
Ethene (C 2H 4)
Propylene (C 3H 6)
Benzene (BNZ)
Octane (NC 8)
1,3-butadiene (C 4H 6)
Testing apparatus and step
Be used for exhaust gas dilution and collection, and all devices of gaseous state regulated emissions concentration analysis is all consistent with the specification that the 91/441/EEC of Directive70/220/EEC revises.
Use the DC type chassis ergograph of Froude Consine manufacturing and the discharge measuring system of Pierburg GmbH (FRG).
Test is carried out under normal probe temperature (+23 ℃).Partly move three times and vehicle is anticipated by EUDC, and before test, under probe temperature, absorb 12-16 hour test.
Table 5 is listed in the chassis ergograph setting that is used for vehicle
Table 5. chassis ergograph is provided with
Inertia 1360kg
F 0 7
F 1 0
F 2 0.046
The gas phase regulated emissions is divided into three subcycles.First part comprises two independent subcycles of city round-robin head, ECE15 (being labeled as phase 1), second is ECE15 round-robin rest part (being labeled as phase 2) mutually, and third part is the extra city part of present European test loop (being labeled as 91/441/EEC) (being labeled as phase 3).
Utilization by AB Svensk Biprovning Motocenter (Swedish Engine and MOT test center) at the diesel oil of thinking in Europe to clean the most, comprise that some kinds of fuel compositions of Swedish Mk1 diesel oil carry out the result that similar test obtained, by Sekab, each result who tests is compared.
Show at the contrast shown in Bi07/ ethanol/diesel oil emission test result: the discharge of all measurements all obviously descends, the CO comprising-20% 2The NO of ,-30% xWith-70% particulate matter.
After initial test five months, VTT takes out the fuel sample that always keeps and it is carried out some test, and test result is enclosed.As can seeing in this test, sample still keeps clean and stablizes after during this period of time, and significantly not rotten.
The result
AAE01/ ethanol/diesel oil blend
The emission test result
CO HC Nox CO2 Particulate matter
g/kWh g/kWh g/kWh g/kWh g/kWh
Mk1 0.61 0.47 6.95 1085 0.2
Mk2 0.61 0.5 7.14 1053 0.21
RME 0.49 0.09 8.99 1053 0.21
Mk1+5％RME 0.62 0.44 7.16 1054 0.2
Mk2+30％RME 0.58 0.33 7.8 1068 0.19
AAE01 Diesohol 0.55 0.21 4.9 863.6 0.056
With the correlated AAE01 diesohol of Mk1 diesel oil
CO HC Nox CO2 Particulate matter
g/kWh g/kWh g/kWh g/kWh g/kWh
Mk1 Diesel 0.61 0.47 6.95 1085 0.2
AAE01 Diesohol 0.55 0.21 4.9 863.6 0.056
Reduce 10％ 55％ 29％ 20％ 72％
Fuel specification
1 grade of diesel oil fuel of Mk1-Scandinavia environment
2 grades of diesel oil fuels of Mk2-Scandinavia environment
RME-Semen Brassicae campestris methyl esters
AAE01-4.25-94.5%Mk1+5% ethanol (90% grade)+0.5-0.75%AAE01 (the equal by volume of all %)
All tests are all carried out on the II low emission level engine of VOLVO Europe.

Claims (42)

1. one kind comprises alkanolamide, the pure and mild ethoxylation C of ethoxylation 18-C 22The fuel additive composition of lipid acid or derivatives thereof, described derivative is selected from the mixture of ester or acid and ester, wherein the ethoxylation degree of lipid acid is that the 0.5-5 mole ethoxylate is to 1 moles of fatty acids, said composition contains the ethoxylated alcohol of the 50 volume % that have an appointment, and the volume content of ethoxylated fatty acid and alkanolamide is basic identical.
2. according to the fuel additive composition of claim 1, it is characterized in that alkanolamide is a glycollic amide.
3. according to the fuel additive composition of claim 2, it is characterized in that alkanolamide is a diglycollic amide.
4. according to the fuel additive composition of claim 3, it is characterized in that diglycollic amide is super diglycollic amide.
5. according to the fuel additive composition of claim 3, it is characterized in that nitrogen in the diglycollic amide is by C 5-C 20Alkyl substituent replaces.
6. according to the fuel additive composition of claim 5, it is characterized in that diglycollic amide is by C 8-C 18Alkyl replaces.
7. according to the fuel additive composition of claim 6, it is characterized in that diglycollic amide is by C 10-C 18Alkyl substituent replaces.
8. according to the fuel additive composition of claim 7, it is characterized in that diglycollic amide is an oleic acid diethyl amide.
9. according to the fuel additive composition of claim 1, it is characterized in that ethoxylated alcohol is an oil soluble alcohol.
10. according to the fuel additive composition of claim 1, it is characterized in that ethoxylated alcohol is an alkanol.
11., it is characterized in that ethoxylated alcohol is a primary alkanol according to the fuel additive composition of claim 10.
12. the fuel additive composition according to claim 10 is characterized in that, alkanol is C 5-C 22Alkanol.
13., it is characterized in that ethoxylated alcohol comprises the mixture that wherein a kind of alkanol accounts for leading alkanol according to the fuel additive composition of claim 10.
14. according to the fuel additive composition of claim 10, it is characterized in that accounting for leading alkanol is C 9-C 11Alkanol.
15. according to the fuel additive composition of claim 1, the ratio that it is characterized in that ethoxylate and alcohol is between 1 and 10.
16. according to the fuel additive composition of claim 15, the ratio that it is characterized in that ethoxylate and alcohol is between 1 and 5.
17. according to the fuel additive composition of claim 16, the ratio that it is characterized in that ethoxylate and alcohol is between 2 and 3.
18., it is characterized in that the ethoxylate and the ratio of alcohol are 2.75 according to the fuel additive composition of claim 17.
19., it is characterized in that lipid acid exists with oleic form according to the fuel additive composition of claim 1.
20., it is characterized in that fatty acid ethoxylate exists with the form of fatty acid ester ethoxylate according to the fuel additive composition of claim 1.
21., it is characterized in that fatty acid ester is the oleic acid alkyl ester according to the fuel additive composition of claim 20.
22., it is characterized in that ethoxylation degree is 1 according to the fuel additive composition of claim 1.
23., it is characterized in that described composition comprises the oleic acid ethoxylate of 25%v/v according to the fuel additive composition of claim 19.
24. fuel composition that comprises the fuel additive composition of liquid hydrocarbon fuels and claim 1.
25., it is characterized in that described fuel is diesel oil fuel according to the fuel composition of claim 24.
26., it is characterized in that fuel is the mixture of diesel oil and alcohol according to the fuel composition of claim 25.
27., it is characterized in that alcohol is ethanol according to the fuel composition of claim 26.
28. the fuel composition according to claim 24 is characterized in that, the ratio of fuel dope and fuel is 0.5-50: 1000 v/v.
29. according to the fuel composition of claim 28, the ratio that it is characterized in that fuel dope and fuel is 1: 1000～30: 1000 v/v.
30. the fuel composition according to claim 29 is characterized in that, the ratio of fuel dope and fuel is 1-3: 100 v/v.
31., it is characterized in that fuel is aqueous ethanol/diesel oil blend according to the fuel composition of claim 27.
32. the fuel composition according to claim 31 is characterized in that, the ratio of additive and fuel is 5% v/v at the most.
33. the fuel composition according to claim 27 is characterized in that, fuel is dehydrated alcohol/diesel oil blend.
34. the fuel composition according to claim 33 is characterized in that, the ratio of additive and fuel is 3% v/v at the most.
35. the fuel composition according to claim 24 is characterized in that, fuel is gasoline.
36. the fuel composition according to claim 35 is characterized in that, fuel is gasoline/ethanol blend.
37. the fuel composition according to claim 35 is characterized in that, the ratio of additive and fuel is 5% v/v at the most.
38. the working method of an oil engine comprises the fuel of use according to claim 24.
39.C 18-C 22The application of lipid acid or derivatives thereof in the fuel additive composition of preparation claim 1, wherein said derivative is selected from the mixture of ester or acid and ester.
40. the application according to claim 39 is characterized in that, C 18-C 22Lipid acid is oleic acid.
41.C 18-C 22The application of lipid acid or derivatives thereof in the fuel composition of preparation claim 24, wherein said derivative is selected from the mixture of ester or acid and ester.
42. the application according to claim 41 is characterized in that, C 18-C 22Lipid acid is oleic acid.
CNB018084966A 2000-02-26 2001-02-23 Fuel additive Expired - Fee Related CN100350024C (en)

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US8974553B2 (en) 2012-03-29 2015-03-10 Joseph Ried Miscible diesel fuel ethanol composition
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