CN1886488A - Fuel compositions comprising a c4-c8 alkyl levulinate - Google Patents
Fuel compositions comprising a c4-c8 alkyl levulinate Download PDFInfo
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- CN1886488A CN1886488A CNA2004800353084A CN200480035308A CN1886488A CN 1886488 A CN1886488 A CN 1886488A CN A2004800353084 A CNA2004800353084 A CN A2004800353084A CN 200480035308 A CN200480035308 A CN 200480035308A CN 1886488 A CN1886488 A CN 1886488A
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- levulinic acid
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- alkyl ester
- ester
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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
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
Abstract
A fuel composition comprising a gas oil base fuel and an alkyl levulinate, wherein said alkyl levulinate is a C4_8 alkyl levulinate. The alkyl levulinate is selected from C4_g alkyl levulinates for the purpose of ensuring a phase separation temperature of said fuel composition below a predetermined level.
Description
The present invention relates to contain the fuel composition of gas oil basic fuel and preparation thereof and use, particularly contain levulinate, more specifically be levulinic acid C
4-C
8This based composition of alkyl ester and preparation thereof and application.
Known with two kinds of different fuel element blend together so that improve performance and/or the character such as the motor performance of resulting composition.
Known diesel oil fuel component comprises so-called " biofuel " that is derived from biomaterial.Example comprises levulinate.
At Zh.Prikl.Khim. (Leningrad) (1969) 42 (4), levulinate (ester of levulinic acid) and preparation and particularly methyl esters, ethyl ester, propyl ester, butyl ester and own ester by suitable alcohol and furfuryl acetate are reacted have been described among the 958-9.
WO-A-94/21753 discloses the fuel that is used for oil engine, and comprising gasoline and diesel oil fuel, described fuel contains the C of certain proportion (for example 1-90%v, 1-50%v, preferred 1-20%v)
4-6Ketone group carbonic acid, preferred levulinic acid and C
1-22The ester of alcohol.According to stating and C
1-8The ester of alcohol is particularly suitable for being included in the gasoline, and and C
9-22The ester of alcohol then is particularly suitable for being included in the diesel oil fuel.
Embodiment in WO-A-94/21753 all comprises a large amount of levulinates in gasoline, in order to improve octane value (RON and MON).
WO-A-03/002696 discloses a kind of fuel composition that mixes levulinic acid or its functional derivatives, its objective is that for example MTBE or ETBE compare with ethanol or conventional oxygenate, the oxygen of more volumes is provided, thereby the Reid vapour pressure increase of fuel seldom or is not increased, and very little or not influence to the flash-point influence of basic fuel.Functional derivatives is alkyl derivative preferably, more preferably C
1-10Alkyl derivative.It is said preferred ethyl levulinate, and methyl ester levulinate is preferred surrogate.Preferred levulinic acid or its functional derivatives of using, the 0.1-5%v of formation fuel.
Although WO-A-03/002696 (the 11st page of the 31st row) has described " setting forth aforementioned content by following embodiment ", it is formed and the test-results data are made up of following sentence:
" particularly, the blended into gasoline thing of finding to contain the nonionogenic tenside of maximum 5.0% ethyl levulinate, 1.0% water and 2.0% has the RVP similar with base gasoline " and
" particularly, the diesel blend thing of finding to contain the nonionogenic tenside of maximum 5.0% ethyl levulinate, 1.0% water and 2.0% has and the similar flash-point of basic diesel oil ".
Present commercially available compression ignite (diesel oil) engine tends to have operation best on the fuel of required specification.In addition, require the condition of power operation can influence the behavior of engine internal fuel composition.Especially, when free air temperature descended, the compatibility between the component in fuel composition can deterioration.When phase separation temperature increased, itself can highlight the deterioration of this compatibility, the temperature when mixture separation became different immiscible layer when wherein said phase separation temperature was defined as cooling.Therefore, normal business diesel base fuel and other fuel element blend may have negative impact to the performance that blend is intended for use in the engine in it to improve overall fuel performance and/or character.
When engine utilizes fuel blends rather than standard base operating fuel, may produce more complicated situation.In the fuel injection system of engine, fuel contacts with the sealing member of great number of elastic material, particularly petrolift.In use, meeting swelling when these elastomericss contact with diesel oil fuel mostly, its degree depends on chemistry of fuel, plays the aromatics fuel element and the oxygenate that for example promote swelling action.
Novel elastomer in the fuel injection system tends to reach balance with uniform fuel formulation (diet), therefore can provide seal degree desired reasonable denseness.But if fuel formulation changes any considerable change that causes the elastomerics degree of swelling, then they become fragile.In the worst case, mixed fuel formula can make the elastic element in the engine be under the strained condition, and its degree makes that fuel takes place to be leaked.
For above-mentioned reasons, wish that the various diesel fuel blends has the cumulative specification that approaches the standard available commercial diesel base fuel as far as possible, because engine tends to be optimized at described standard available commercial diesel base fuel.
But this may be difficult to realize, because any additional fuel element all may change the performance and the character of basic fuel.In addition, the performance of blend, particularly it can be according to the performance simple forecast of independent fuel composition to the elasticity engine components with to the influence of low-temperature performance.
Now be surprisingly found out that, in the fuel composition that contains gas oil basic fuel and levulinic acid alkyl ester, from levulinic acid C
4-8Select described levulinic acid alkyl ester can guarantee that the phase separation temperature of described fuel composition is lower than predeterminated level in the alkyl ester.Also be surprisingly found out that, compare, contain levulinic acid C with this fuel composition of the ethyl levulinate that contains similar concentration
4-8The described fuel composition of alkyl ester is more compatible with some elaxtic seals, and wherein said consistency is not obviously to be different from basic fuel.
For example find, if be blended into the interior 5%v ethyl levulinate of certain basic fuel by some levulinic acid C of 5%v
4-8Alkyl ester alternate words, then phase separation temperature descends greatly, promptly improves the compatibility between basic fuel and the levulinate.When fuel blends was used under the low temperature environment in the engine of operation, this may be very favorable certainly.In addition, find, compare, contain levulinic acid C with the blend that contains ethyl levulinate
4-8The described blend of alkyl ester has significantly less influence to elastomeric swelling and hardness.
According to the present invention, a kind of fuel composition is provided, it comprises gas oil basic fuel and levulinic acid alkyl ester, wherein said levulinic acid alkyl ester is levulinic acid C
4-8Alkyl ester.Preferably, described levulinic acid alkyl ester is selected from levulinic acid C
4-8Alkyl ester, for example positive butyl ester of levulinic acid, levulinic acid n-pentyl ester, the own ester of levulinic acid 2-and levulinic acid 2-ethylhexyl are lower than predeterminated level in order to ensure the phase separation temperature of described fuel composition.Described level preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.Preferably, described levulinic acid alkyl ester is selected from levulinic acid C
4-6Alkyl ester more preferably is selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, and perhaps described levulinic acid alkyl ester is levulinic acid C
5Alkyl ester.In described fuel composition, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
According to the present invention, also provide levulinic acid C
4-8Alkyl ester is as the purposes of described levulinic acid alkyl ester in the fuel composition that comprises gas oil basic fuel and levulinic acid alkyl ester, is lower than predeterminated level in order to ensure the phase separation temperature of described fuel composition.Described level preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.Preferably, in described purposes, described levulinic acid alkyl ester is selected from levulinic acid C
4-6Alkyl ester more preferably is selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, and perhaps described levulinic acid alkyl ester is levulinic acid C
5Alkyl ester.In described purposes, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
According to the present invention, advance-go on foot the method that the phase separation temperature that reduces the fuel composition that contains gas oil basic fuel and ethyl levulinate is provided, described method comprises uses levulinic acid C
4-8Alkyl ester substitutes to the described ethyl levulinate of small part.Described method preferably includes and reduces phase separation temperature and be lower than predeterminated level, described level preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.
According to the present invention, the operating compression ignition engine still further is provided and/or utilizes the method for this engine-driven vehicle, described method comprises fuel composition of the present invention is incorporated in the combustion chamber of engine.
According to the present invention, still further provide operation to be furnished with the method for the heating installation of burner, described method comprises supplies with described burner with fuel composition of the present invention.
According to the present invention, the method for preparing fuel composition still further is provided, this method comprises blend gas oil basic fuel and levulinic acid C
4-8Alkyl ester.Preferably, in described method, described levulinic acid alkyl ester is selected from levulinic acid C
4-6Alkyl ester more preferably is selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, and perhaps described levulinic acid alkyl ester is levulinic acid C
5Alkyl ester.In described method, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
Of the present invention aspect all in, can comprise two or more levulinic acids C in the fuel composition
4-8The blend of alkyl ester, for example blend of positive butyl ester of levulinic acid and levulinic acid n-pentyl ester.In the context of the present invention, one or more required features of fuel composition are depended in the selection of the specific components of described blend and ratio thereof.
Can use preparation of fuels blend of the present invention, expect that described fuel blends can be used in particular in the current commercially available diesel motor substitute as the standard diesel base fuel, for example when pressure commercial and legislation helps using organic deutero-" biofuel " of increasing amount.
In the context of the present invention, " purposes " of fuel element in fuel composition be meant before being incorporated into said composition in the engine routinely, and this component is incorporated in the said composition as the form with the blend (being physical mixture) of one or more other fuel elements.
Fuel composition typically contains the basic fuel of main ratio, for example 50-99%v, preferably 50-98%v, more preferably 80-98%v, most preferably 90-98%v.Select levulinic acid C
4-8The ratio of alkyl ester is to realize that required miscible degree is that phase separation temperature and elastomerics swelling and hardness effect and this ratio also may be subjected to desired other performance impact of total composition.
Influence to the elasticity engine components can comprise for example diesel motor inside in associated fuel is introduced it, changes the physicals (for example volume, hardness and/or flexible) that contacts, soaks given resilient material within it suitably with relevant fuel or fuel composition.Typically, this variation comprises that volume increases and/or hardness descends.These can use the standard test operation to measure, and for example BS903, SATM D471, D2240 or IS01817:1998 are for example described in following examples 2.Can assess with respect to nitrile (comprising hydrogenated nitrile) elastomerics or fluorocarbon elastomer especially.
Preferably, levulinic acid C
4-8Alkyl ester is included in the fuel composition, and its ratio for example causes any given resilient material (fluorohydrocarbon class such as LR6316 (ex.James Walker ﹠amp for example; Co., Ltd., UK)) volume change can obviously not be different from the volume change that is caused by basic fuel when testing under the same terms.
Preferably, levulinic acid C
4-8Alkyl ester is included in the fuel composition, and its ratio for example causes that the changes in hardness of any given resilient material (for example fluorohydrocarbon class for example LR6316) can obviously not be different from the changes in hardness that is caused by basic fuel when testing under the same conditions.Still more preferably, this ratio for example realizes that the elastomerics changes in hardness is not higher than independent basic fuel, is desirably 95% or 90% or 85% or lower of changes in hardness that basic fuel causes.
Fuel composition involved in the present invention is included in diesel oil fuel that uses in automatic compression-ignition engine and other type of engine such as navigation, railway and the stationary engine and the industrial gas oil of using in heating installation (for example boiler).
Basic fuel itself can comprise the mixture of two or more different diesel oil fuel components, and/or interpolation additive as described below.
This diesel oil fuel contains basic fuel, and described basic fuel typically can comprise liquid hydrocarbon middle runnings gas oil, for example gas oil of petroleum derivation.Depend on grade and purposes, the boiling point of this fuel is typically in 150-400 ℃ common diesel range.Their density under 15 ℃ typically is 750-900kg/m
3, preferred 800-860kg/m
3(for example ASTM D4502 or IP365), and cetane value (ASTM D613) is 35-80, more preferably 40-75.Typically their initial boiling point scope is that 150-230 ℃ and full boiling point scope are 290-400 ℃.Their kinematic viscosity (ASTM D445) under 40 ℃ may suitably be 1.5-4.5mm
2/ s.
This industrial gas oil contains basic fuel, and described basic fuel can comprise fuel fraction, for example kerosene that in conventional refinery technology, obtains or gas oil fraction, and the quality that these cuts improve the raw petroleum raw materials makes it to become useful product.Preferably, this cut contain carbon number range be 5-40, more preferably 5-31, still more preferably 6-25, most preferably component and the density of this cut under 15 ℃ of 9-25 are 650-950kg/m
3, the kinematic viscosity under 20 ℃ is 1-80mm
2/ s and boiling range are 150-400 ℃.
Randomly, non-mineral oil base fuel, biological example fuel or Fisher-Tropsch derived fuel also can form or be present in this fuel composition.
The amount of employed Fisher-Tropsch derived fuel can be the 0.5-100%v of whole diesel fuel composition in diesel oil fuel, preferred 5-75%v.It is desirable to said composition and contain Fisher-Tropsch derived fuel more than or equal to 10%v, more preferably greater than or equal 20%v, still more preferably greater than or equal 30%v.Special preferred composition contains Fisher-Tropsch derived fuel and particularly 30%v or the 70%v of 30-75%v.The surplus of fuel composition is by one or more other fuel compositions.
The industrial gas oil composition preferably includes greater than 50wt%, more preferably greater than the Fisher-Tropsch derived fuel element of 70wt%.
This Fisher-Tropsch derived fuel element is any cut of midbarrel fuel scope, it can be separated with (hydrocracking) fischer-tropsch synthesis product.The boiling point of typical case's cut is in the boiling range of petroleum naphtha, kerosene or gas oil.The fischer-tropsch products of preferred use boiling point in kerosene or gas oil boiling range is because these products for example are being more prone to handle in the commercial environment.This product comprise suitably greater than the boiling point of 90wt% between 160-400 ℃, preferably to about 370 ℃ cut.The Fisher-Tropsch derived kerosene and the example of gas oil have been described in EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648, WO-A-01/83647, WO-A-01/83641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, US-A-5766274, US-A-5378348, US-A-5888376 and US-A-6204426.
Fischer-tropsch products contains suitably greater than 80wt% with more suitably greater than the different and n-paraffin of 95wt% with less than the aromatic hydrocarbons of 1wt%, and surplus is naphthenic compounds (naphthenics).The content of sulphur and nitrogen is very low, is usually less than the sensing range of these compounds.Owing to this reason, the sulphur content that contains in the fuel composition of fischer-tropsch products may be very low.
Fuel composition preferably contains the sulphur that is not more than 5000ppmw, more preferably no more than 500ppmw, or is not more than 350ppmw, or is not more than 150ppmw, or be not more than 100ppmw, or be not more than 50ppmw, or most preferably be not more than the sulphur of 10ppmw.
Except levulinic acid C
4-8Beyond the alkyl ester, fuel composition of the present invention also can optionally contain the additive of one or more the following stated.
Basic fuel itself can be added with additive (containing additive) or not add additive (not containing additive).If be added with the words of additive, then for example in oil refining factory and office, it will contain trace one or more for example be selected from static inhibitor, pipeline drag force depressant, FLOW IMPROVERS (for example ethylene or acrylate/copolymer-maleic anhydride) and paraffin antisettling agent (for example with trade(brand)name " PARAFLOW " (PARAFLOW for example
TM450, ex Infineum), " OCTEL " (OCTEL for example
TMW 5000, ex Octel) and " DODIFLOW " (DODIFLOW for example
TMV 3958, ex Hoechst) be purchased those) in additive.
The diesel fuel additive that contains sanitising agent is known, and can for example be available commercially from Infineum (for example F7661 and F7685) and Octel (for example OMA 4130D).Can be with this additive only to reduce or the low relatively amount of engine deposits cumulative that slows down joins in the diesel oil fuel (in being added with the whole fuel composition of additive, its " standard " is handled flow active substance sanitising agent less than 100ppmw typically is provided).
For purpose of the present invention, the example of the sanitising agent that is suitable for using in fuel dope comprises the succinimide or the succinic diamide of the polyamines that polyolefine replaces, for example polyisobutenyl succinimide or polyisobutylene amine succinamides, aliphatic amine, Mannich base or amine and polyolefine (for example polyisobutene) maleic anhydride.For example among GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and the WO-A-98/42808 succinimide dispersant additives is being described.Particularly preferably be the succinimide that polyolefine replaces, for example polyisobutenyl succinimide.
Additive also can contain other component except that sanitising agent.Example is the lubricity toughener; Demisting agent, alkoxylate novolac polymer for example is for example with NALCO
TMEC5462A (being 7D07 in the past) (ex Nalco) and TOLAD
TMThose that 2683 (ex Petrolite) are purchased; Defoamer is (for example with TEGOPREN
TM5851 and the polyether-modified polysiloxane that is purchased of Q25907 (ex Dow Corning), SAG
TMTP-325 (ex OSi) and RHODORSIL
TM(ex RhonePoulenc)); Ignition improver (n-Hexadecane improving agent) (for example nitric acid 2-ethylhexyl (EHN), cyclohexyl nitrate, di-t-butyl peroxide and in the 2nd hurdle 27-the 3rd hurdle of US-A-4208190 the 21st row those disclosed); Rust-preventive agent is (for example by Rhein Chemie, Mannheim, Germany is with " RC 4801 " commercially available those), the third-1 of tetrapropylene base succsinic acid, 2-glycol half ester, the perhaps polyol ester of succinic acid derivative, wherein succinic acid derivative has the aliphatic hydrocarbyl that does not replace or replace that contains 20-500 carbon atom on its at least one alpha-carbon atom, for example the pentaerythritol diester of the succsinic acid that replaces of polyisobutene); Sanitas; Reodorant; Anti-wear additive; Antioxidant (phenols for example, for example 2,6 di t butyl phenol, or phenylenediamine, N for example, N '-di-sec-butyl-p-phenyl enediamine); And metal passivator.
Special have low sulphur content when (for example being less than or equal to 500ppmw) when fuel composition, and preferable additives comprises the lubricity toughener especially.In being added with the fuel composition of additive, the lubricity toughener exists with the concentration between 50-1000ppmw routinely, preferably between 100-1000ppmw.Suitable commercially available lubricity toughener comprises EC832 and PARADYNE
TM655 (ex Infineum), HITEC
TME580 (ex Ethyl Corporation), VEKTRON
TM6010 (ex Infineum) and amide group additives for example are available commercially from those of LubrizolChemical Company, for example LZ 539C.In following patent documentation for example, special in the use in the diesel oil fuel of low sulfur content, other lubricity toughener has been described:
The paper of-Danping Wei and H.A.Spikes, " The Lubricity of DieselFuels ", Wear, III (1986), 217-235;
-WO-A-95/33805-improves the cold flow improving agent of low-sulfur fuel oilness;
The ester of some carboxylic acids of-WO-A-94/17160-and alcohol, wherein acid has 2-50 carbon atom, have more than or equal to 1 carbon atom with alcohol, special XU 61518.10 and the diisodecyl adipate additive that acts as a fuel is used to reduce the wearing and tearing of diesel motor injection system;
-US-A-5484462-mentions that linoleic acid dimer provides the aminoalkyl group morpholine lubrication modifier that acts as a fuel as the commercially available lubricant of low sulphur diesel fuel (the 1st hurdle the 38th row) and itself;
Some phosphorodithioic acid diester-glycol of-US-A-5490864-are as the wear-resisting slip additive of low sulphur diesel fuel; With
Some have the Alkylaromatics that at least one is connected to the carboxyl on its virtue nuclear-WO-A-98/01516-, so that give low sulphur diesel fuel attrition resistant lubricant effect especially.
Also preferable additives contains defoamer, more preferably makes up rust-preventive agent and/or sanitas and/or slip additive.
Except as otherwise noted, the preferred 10000ppmw at most of (active substance) concentration of each such annexing ingredient in being added with the fuel composition of additive, more preferably 5-1000ppmw advantageously is 75-300ppmw, for example 95-150ppmw.
(active substance) concentration range of any demisting agent in fuel composition is preferably 1-20ppmw, more preferably 1-15ppmw, and still more preferably 1-10ppmw advantageously is 1-5ppmw.(active substance) concentration of any ignition improver is preferably and is less than or equal to 600ppmw, is more preferably less than or equals 500ppmw, is suitably 300-500ppmw.
Optionally, binder component listed above can be preferably with the suitable diluent blend in multifunctional additive for lubricating oils and multifunctional additive for lubricating oils can be distributed in the fuel with appropriate vol, form composition of the present invention.
Under the situation of diesel oil fuel, for example additive typically contains sanitising agent, choose wantonly and contain above-described other component together, and the thinner compatible with diesel oil fuel, described thinner can be carrier oil (a for example mineral oil), polyethers (it can by end-blocking or not by end-blocking), non-polar solvent such as toluene, dimethylbenzene, petroleum solvent, with sell with trade(brand)name " SHELLSOL " by the Subsidiary Company of Royal Dutch/Shell Group those, and/or polar solvent, ester for example, particularly pure, hexanol for example, 2-Ethylhexyl Alcohol, decyl alcohol, the mixture of different 13 carbon alcohol and alcohol for example by the Subsidiary Company of Royal Dutch/Shell Group with trade(brand)name " LINEVOL ", LINEVOL particularly
TM(it is C to 79 alcohol
7-9The mixture of primary alconol) those of Xiao Shouing, perhaps commercially available in the C of French Sidobre Sinnova with " SIPOL "
12-14Alcohol mixture.
Additive level can be suitably between 0-10000ppmw with preferably be lower than 5000ppmw.
Preferably, the levulinic acid C in the fuel composition
4-8The concentration of alkyl ester meets one or more following parameters:
(i) 1%v at least; (ii) 2%v at least; (iii) 3%v at least; (iv) 4%v at least; (v) maximum 6%v; (vi) maximum 8%v; (vii) maximum 10%v; (viii) maximum 12%v;
Has feature (i) and (viii), (ii) and (vii), (iii) and (vi) and (iv) and (scope v) is progressively preferred respectively.
In this manual, (ppmw wt%) is meant active substance to components contents for concentration, %v, does not promptly comprise volatile solvent/diluent material.
The present invention is specially adapted to wherein that fuel composition is used for or intends being used for directly injecting diesel motor for example rotary pump, online pump, modular pump, electronic unit syringe or common rail type, perhaps injects indirectly under the situation of diesel motor.For the rotary pump engine with in mechanically operated other diesel motor that depends on fuel injector and/or low pressure guiding injection system, it is valuable especially.This fuel composition can be suitable in heavy type and/or the light-duty diesel engine.
It can be applicable to also wherein that fuel composition is used for for example situation of boiler of heating installation, comprising standard boiler, low temperature boiler and condensing boiler.This boiler typically is used to add hot water for commerce or household application, for example the heating of space heating and water.
The present invention can cause any in many advantageous effects, comprising good engine low-temperature performance.
By describing the present invention with reference to following embodiment:
By in envrionment temperature (20 ℃) thus add down additive in basic fuel and homogenizing blended fuels and additive.
Use following additives: ethyl levulinate (available from ex.Avocado); The positive butyl ester of levulinic acid (available from ex.Aldrich); Levulinic acid n-pentyl ester (available from ex.City Chemical or by 1-amylalcohol (available from ex.Aldrich) and levulinic acid (available from ex.Aldrich) reaction are obtained); The own ester of levulinic acid 2-(by 1-hexene (available from ex.Fluka) or 2-hexanol (available from ex.Aldrich) and levulinic acid prepared in reaction).
Embodiment 1
The compatibility of levulinic acid alkyl ester in diesel oil fuel (AGO)
The compatibility of levulinate is somewhat dependent upon the performance of basic fuel.Select three kinds of representative basis fuel of European market, study this effect, promptly (1) fuel A is the diesel oil fuel (ULSD) of super low sulfur, and this is typical 2005 European diesel fuel specifications, and its cloud point is 25%m for-8 ℃ with aromaticity content; (2) fuel B is Dreyfuss ULSD, and it is a kind of AGO of hydrotreatment, its have lower cloud point (27 ℃) and with aromaticity content (22%m) like the fuel category-A, it meets European specification EN590; (3) fuel C is Swedish Class 1 AGO, and it is the diesel oil fuel of a kind of low density, low aromatic hydrocarbons (4%m), and in these three kinds of basic fuels cloud point minimum (38 ℃).
Provided the performance of fuel A, B and C in the table 1.
Table 1
| Fuel A | Fuel B | Fuel C | |
| Density kg/m under 15 ℃ 3 | 834 | 822 | 815 |
| Distillation T50, ℃ | 280 | 242 | 235 |
| Distillation T95, ℃ | 343 | 304 | 272 |
| Cetane value | 56 | 54 | 54 |
| Viscosity under 40 ℃, mm 2/s | 2.91 | 2.10 | 2.03 |
| Sulphur, mg/kg | 38 | 10 | ＜5 |
| Cloud point, ℃ | -8 | -27 | -38 |
| Aromatic hydrocarbons, %m | 25 | 22 | 4 |
In order to screen purpose, use the simple experiment method, to measure the miscible limit of room temperature (20 ℃) of ethyl levulinate.In the 15ml vial, the ester of accurate measurement volume is joined in the diesel oil fuel of known volume according to the order of sequence, shake and observe.Record occurs muddy as the miscible limit of the room temperature of this mixture first.The result has been shown in the table 2 and has clearly illustrated that fuel C is the most serious in three kinds of basic fuels being tested.Select this fuel for further miscible test.
Table 2
| Fuel A | Fuel B | Fuel C |
| 10％v | 14％v | 7％v |
Use is measured the compatibility of various levulinic acid alkyl esters based on the method for ASTM D2500 " cloud point " operation.In this operation, in maintaining a series of thermostatic baths that progressively reduce under the temperature, from envrionment temperature (20 ℃) cooling fuel sample (40ml).When being cooled to its wax cloud point, with 1 ℃ interval test sample.Except the wax cloud point temperature described in the ASTM D2500,, then write down and two other consistent temperature of following observation if they following situation occurs:
(1) muddiness appears first,
(2) separate first signal that liquid phase is separated out.
Under each situation, continue to be cooled to wax cloud point-be higher than under the situation of wax cloud point, can not observe further reliably and be separated.
In fuel C,, and measure the compatibility of each blend with the solution of various concentration blend ethyl levulinates, the positive butyl ester of levulinic acid and levulinic acid n-pentyl ester.In the following table 3 result has been shown.
Table 3
| Phase separation temperature (℃) | |||
| The concentration of ester (%v) | Ethyl levulinate | The positive butyl ester of levulinic acid | The levulinic acid n-pentyl ester |
| 1 | -37 | - | - |
| 2 | -26 | -38 | -38 |
| 3 | -10 | -37* | -38* |
| 4 | 3 | -36 | -38 |
| 5 | 5 | -31* | -38* |
| 6 | - | -26 | -38 |
| 8 | - | -22 | -33 |
| 10 | - | -18 | -28 |
* extrapolated value
As can be seen from Table 3, positive butyl ester of levulinic acid and levulinic acid n-pentyl ester all have the compatibility that is better than ethyl levulinate in fuel C.For example under the ethyl levulinate of 5%v, phase separation temperature is 5 ℃, and under positive butyl ester of the levulinic acid of 5%v or levulinic acid n-pentyl ester, phase separation temperature is lower than-30 ℃.Be noted that up to the levulinic acid n-pentyl ester concentration of 8-10%v with up to maintenance solution forms under the levulinic acid n-pentyl ester concentration of 10%v is being lower than-20 ℃ at least, even in this harsh Swedish Class 1 AGO.
Use fuel B to repeat the compatibility test, this discovery of proof in the diesel oil fuel of more conventional European EN590 specification.These results have been shown in the table 4.
Table 4
| Phase separation temperature (℃) | |||
| The concentration of ester (%v) | Ethyl levulinate | The positive butyl ester of levulinic acid | The levulinic acid n-pentyl ester |
| 2 | - | -28 | -27 |
| 3 | -27 | -27* | -27* |
| 4 | -17 | -27 | -27 |
| 5 | -10 | -27* | -27* |
| 6 | -5* | -28 | -27 |
| 8 | 7 | -27 | -26 |
| 10 | 14 | -27 | -28 |
* extrapolated value
As can be seen from Table 4, positive butyl ester of levulinic acid and levulinic acid n-pentyl ester under 4%v and above concentration, have the compatibility that is better than ethyl levulinate in fuel B.For example under the ethyl levulinate of 5%v, phase separation temperature is-10 ℃, and under positive butyl ester of the levulinic acid of 5%v or levulinic acid n-pentyl ester, phase separation temperature is-27 ℃.Be noted that being lower than-20 ℃ up to the positive butyl ester concentration of levulinic acid of 10%v at least and levulinic acid n-pentyl ester concentration keeps the solution forms down, and reach the wax cloud point before being separated observing.
Embodiment 2
The levulinic acid alkyl ester influences the fluorocarbon elastomer swollen
Use is assessed the influence of various levulinic acid alkyl ester compounds to elastomeric seal based on the The test procedure of IS01817:1998.Under envrionment temperature (20 ℃), dipping was measured the volume and the average Shore hardness of the elastomer sample that is nominally 50mm * 25mm * 3mm thickness before with afterwards in 168 hours in the 100ml test fuel.Afterwards, take out sample from test fluid, the accelerated surface drying is weighed in empty G﹠W, is taking out new volume and the hardness of measuring them in 8 hours from test(ing) medium.Use Type A Shore
TM(ShoreInstruments USA), measures hardness to Durometer at ambient temperature.Then for each sample, record is because of being exposed to the volume that causes under the test fuel and the percent change of average hardness.
Test, to compare ethyl levulinate, the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-elastomeric influence.Under the concentration of 5%v in these compounds each is blended in the basic fuel fuel D, fuel D is a kind of diesel fuel sample of routine.Table 5 shows the performance of fuel D and the blend of 5%v levulinic acid n-pentyl ester in fuel D.
Table 5
| Performance | The EN590:2000 specification | Fuel D | 5%v levulinic acid n-pentyl ester in fuel D |
| Density kg/m under 15 ℃ 3 | 820-845 | 834.2 | 841.1 |
| Distillation | |||
| IBP | 179.7 | 185.0 | |
| 10％ | 215.2 | 217.0 | |
| 20％ | 236.7 | 234.5 | |
| 30％ | 254.0 | 250.0 | |
| 40％ | 268.6 | 264.0 | |
| 50％ | 280.3 | 276.5 | |
| 60％ | 290.4 | 288.5 | |
| 70％ | 300.4 | 299.5 | |
| 80％ | 311.6 | 311.5 | |
| 90％ | 326.7 | 328.0 | |
| 95％ | 360max | 338.9 | 343.5 |
| FBP | 353.1 | 352.0 | |
| Reclaim %v down at 240 ℃ | 22.4 | 23.5 | |
| Reclaim %v down at 250 ℃ | 65max | 27.6 | 30.0 |
| Reclaim %v down at 340 ℃ | 95.3 | 94.0 | |
| Reclaim %v down at 345 ℃ | 96.7 | 95.5 | |
| Reclaim %v down at 350 ℃ | 85min | 97.9 | 96.5 |
| Cetane value | 51min | 55.2/54.8 | 53.4 |
| Viscosity under 40 ℃, mm 2/s | 2-4.5 | 2.910 | 2.884 |
| Sulphur, mg/kg | 350 | 38 | - |
| Lubricity (HFRR wear print, μ m) | ＜460 | 302/298 | - |
| Flash-point, ℃ | ＞55 | 67 | 74.5 |
| Peroxide level, ppm | Record | 0.5 | 0.8 |
Select the representative (0-shape ring etc.) of following resilient material as the sealing member that uses in current diesel oil fuel system: (the fluorohydrocarbon tetramer is also referred to as Viton (trade(brand)name) (exJames Walker ﹠amp to LR6316; Co.Ltd., UK)).Select it as the typical elastomeric of using in current diesel oil fuel system, although compare with some other resilient materials, its sealing member swelling is less sensitive, can give prominence to the considerable change of swelling behavior.
Various levulinic acid ester blends have been summarized in the table 6 to the volume of LR6316 fluorocarbon elastomer sample and the influence of hardness.
Table 6
| Component/blend | The %v oxygenate | The % volume change | The % changes in hardness |
| Fuel D | 0 | 0.02 | -1.3 |
| Ethyl levulinate | 5 | 10.63 | -14.4 |
| The positive butyl ester of levulinic acid | 5 | 2.4 | -0.4 |
| The levulinic acid n-pentyl ester | 5 | 1.7 | -0.83 |
| The own ester of levulinic acid 2- | 5 | 1 | 0 |
As can be seen, compare with ethyl levulinate, the own ester of the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and levulinic acid 2-produces obviously less sealing member swelling (being the % volume change); And the changes in hardness of the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-is significantly less than ethyl levulinate and obviously is not different from conventional oil D.
The ISO1817 standard is clear have been described " imply with usage behavior and do not have direct correlation ", therefore, under not having with reference to last situation about using, can not define " qualified/failure " threshold value.But if thinking to demonstrate for the LR6316 fluorocarbon elastomer is less than or equal to 2% sealing member swollen fuel or fuel dope can not cause the use problem, then levulinic acid n-pentyl ester and the own ester of levulinic acid 2-are preferred levulinates as can be seen from Table 6.
Claims (10)
1. fuel composition, it comprises gas oil basic fuel and levulinic acid alkyl ester, wherein said levulinic acid alkyl ester is levulinic acid C
4-8Alkyl ester.
2. the fuel composition of claim 1, wherein said levulinic acid alkyl ester is selected from levulinic acid C
4-8Alkyl ester is lower than predeterminated level in order to ensure the phase separation temperature of described fuel composition, and described level is preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.
3. claim 1 or 2 fuel composition, wherein said levulinic acid alkyl ester is selected from levulinic acid C
4-6Alkyl ester be preferably selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, or wherein said levulinic acid alkyl ester is levulinic acid C
5Alkyl ester, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
4. levulinic acid C
4-8Alkyl ester in the fuel composition that contains gas oil basic fuel and levulinic acid alkyl ester as the purposes of described levulinic acid alkyl ester, phase separation temperature in order to ensure described fuel composition is lower than predeterminated level, described level is preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.
5. the purposes of claim 4, wherein said levulinic acid alkyl ester is selected from levulinic acid C
4-6Alkyl ester be preferably selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, or wherein said levulinic acid alkyl ester is levulinic acid C
5Alkyl ester, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
6. reduce the method for the phase separation temperature of the fuel composition that contains gas oil basic fuel and ethyl levulinate, this method comprises uses levulinic acid C
4-8Alkyl ester substitutes to the described ethyl levulinate of small part.
7. the method for claim 6, it comprises that reducing phase separation temperature is lower than predeterminated level, described level is preferably-10 ℃, more preferably-20 ℃ and most preferably-30 ℃.
8. operating compression ignition engine and/or utilize the method for this engine-driven vehicle, this method comprise claim 1,2 or 3 fuel composition are incorporated in the combustion chamber of described engine.
9. operation is furnished with the method for heating installation of burner, and this method comprises that supply claim 1,2 or 3 fuel composition are in described burner.
10. the method for preparing fuel composition, this method comprise blend gas oil basic fuel and levulinic acid C
4-8Alkyl ester, wherein said levulinic acid alkyl ester is preferably selected from levulinic acid C
4-6Alkyl ester more preferably be selected from the positive butyl ester of levulinic acid, levulinic acid n-pentyl ester and the own ester of levulinic acid 2-, or wherein said levulinic acid alkyl ester is levulinic acid C
5Alkyl ester, described levulinic acid alkyl ester is the levulinic acid n-pentyl ester preferably.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03257073.1 | 2003-11-10 | ||
| EP03257073 | 2003-11-10 |
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| CN1886488A true CN1886488A (en) | 2006-12-27 |
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|---|---|---|---|
| CNA2004800353084A Pending CN1886488A (en) | 2003-11-10 | 2004-11-08 | Fuel compositions comprising a c4-c8 alkyl levulinate |
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| Country | Link |
|---|---|
| US (1) | US20050144835A1 (en) |
| EP (1) | EP1685217B1 (en) |
| JP (1) | JP5132937B2 (en) |
| CN (1) | CN1886488A (en) |
| BR (1) | BRPI0416356A (en) |
| CA (1) | CA2545170C (en) |
| NO (1) | NO20062725L (en) |
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| CN107841350A (en) * | 2016-09-18 | 2018-03-27 | 北京特生物化工有限公司 | A kind of bio-based esters micro emulsion diesel fuel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1732876A1 (en) * | 2004-03-24 | 2006-12-20 | E.I.Du pont de nemours and company | Preparation of levulinic acid esters from alpha-angelica lactone and alcohols |
| WO2007012586A1 (en) * | 2005-07-25 | 2007-02-01 | Shell Internationale Research Maatschappij B.V. | Fuel compositions |
| CN101233216A (en) * | 2005-07-25 | 2008-07-30 | 国际壳牌研究有限公司 | Fuel compositions |
| US20090090048A1 (en) * | 2007-10-05 | 2009-04-09 | Board Of Trustees Of Michigan State University | Fuel compositions with mono- or di- butyl succinate and method of use thereof |
| CA2729355A1 (en) * | 2008-07-02 | 2010-01-07 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
| WO2010106536A1 (en) * | 2009-03-16 | 2010-09-23 | Ben-Gurion University Of The Negev Research And Development Authority | Diesel fuel from vegetable and animal oils blended with alkyl levulinates |
| US20100313467A1 (en) * | 2009-06-16 | 2010-12-16 | Meadwestvaco Corporation | Diesel fuel compositions containing levulinate ester |
| CN102796573B (en) * | 2012-07-24 | 2014-09-17 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| BR112016013992A2 (en) | 2013-12-19 | 2017-08-08 | Basf Se | COSMETIC COMPOSITION |
| CA2976084C (en) * | 2015-02-10 | 2020-01-07 | Avantium Knowledge Centre B.V. | Fuel composition comprising humins |
| US20190209451A1 (en) | 2016-07-08 | 2019-07-11 | Basf Se | Solubilizing agents for uv filters in cosmetic formulations |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3563715A (en) * | 1958-07-15 | 1971-02-16 | Chevron Res | Motor fuels |
| US3879176A (en) * | 1970-12-11 | 1975-04-22 | Nippon Oil Co Ltd | Liquefied petroleum gas compositions |
| US4208190A (en) * | 1979-02-09 | 1980-06-17 | Ethyl Corporation | Diesel fuels having anti-wear properties |
| US5290325A (en) * | 1990-02-28 | 1994-03-01 | Union Oil Company Of California | Hydrocarbon fuel composition containing alpha-ketocarboxylate additive |
| US5490864A (en) * | 1991-08-02 | 1996-02-13 | Texaco Inc. | Anti-wear lubricity additive for low-sulfur content diesel fuels |
| DE4308053C2 (en) * | 1993-03-13 | 1997-05-15 | Veba Oel Ag | Liquid unleaded fuels |
| US5378348A (en) * | 1993-07-22 | 1995-01-03 | Exxon Research And Engineering Company | Distillate fuel production from Fischer-Tropsch wax |
| US5484462A (en) * | 1994-09-21 | 1996-01-16 | Texaco Inc. | Low sulfur diesel fuel composition with anti-wear properties |
| US5888376A (en) * | 1996-08-23 | 1999-03-30 | Exxon Research And Engineering Co. | Conversion of fischer-tropsch light oil to jet fuel by countercurrent processing |
| US5766274A (en) * | 1997-02-07 | 1998-06-16 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US6475252B1 (en) * | 1998-09-17 | 2002-11-05 | University Of Dayton | Stabilizing additive for the prevention of oxidation and peroxide formation |
| US6204426B1 (en) * | 1999-12-29 | 2001-03-20 | Chevron U.S.A. Inc. | Process for producing a highly paraffinic diesel fuel having a high iso-paraffin to normal paraffin mole ratio |
| GB0111679D0 (en) * | 2001-05-12 | 2001-07-04 | Aae Tech Int Ltd | Fuel composition |
| GB2387175A (en) * | 2002-03-13 | 2003-10-08 | Shell Int Research | Oxidised fuel formulations |
| JP2005521748A (en) * | 2002-04-01 | 2005-07-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Production of levulinate and formate from biomass and olefins |
| MY140297A (en) * | 2002-10-18 | 2009-12-31 | Shell Int Research | A fuel composition comprising a base fuel, a fischer-tropsch derived gas oil and an oxygenate |
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2004
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- 2004-11-08 BR BRPI0416356-7A patent/BRPI0416356A/en not_active IP Right Cessation
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- 2004-11-08 CN CNA2004800353084A patent/CN1886488A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841350A (en) * | 2016-09-18 | 2018-03-27 | 北京特生物化工有限公司 | A kind of bio-based esters micro emulsion diesel fuel and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP5132937B2 (en) | 2013-01-30 |
| WO2005044960A1 (en) | 2005-05-19 |
| NO20062725L (en) | 2006-06-12 |
| EP1685217B1 (en) | 2012-12-12 |
| JP2007510787A (en) | 2007-04-26 |
| CA2545170A1 (en) | 2005-05-19 |
| ZA200603455B (en) | 2007-08-29 |
| AU2004287631A1 (en) | 2005-05-19 |
| US20050144835A1 (en) | 2005-07-07 |
| CA2545170C (en) | 2013-10-22 |
| EP1685217A1 (en) | 2006-08-02 |
| BRPI0416356A (en) | 2007-03-13 |
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