US20030094397A1 - Clean-burning MTBE-free gasoline fuel - Google Patents

Clean-burning MTBE-free gasoline fuel Download PDF

Info

Publication number
US20030094397A1
US20030094397A1 US10/080,862 US8086202A US2003094397A1 US 20030094397 A1 US20030094397 A1 US 20030094397A1 US 8086202 A US8086202 A US 8086202A US 2003094397 A1 US2003094397 A1 US 2003094397A1
Authority
US
United States
Prior art keywords
vol
content
less
olefins
gasoline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/080,862
Inventor
Jyrki Ignatius
Juha Jakkula
Risto Nasi
Aimo Rautiola
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fortum Oyj
Original Assignee
Fortum Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US31241001P priority Critical
Application filed by Fortum Oyj filed Critical Fortum Oyj
Priority to US10/080,862 priority patent/US20030094397A1/en
Assigned to FORTUM OYJ reassignment FORTUM OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IGNATIUS, JYRKI, NASI, RISTO, RAUTIOLA, AIMO, JAKKULA, JUHA
Publication of US20030094397A1 publication Critical patent/US20030094397A1/en
Application status is Abandoned legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/10Use of additives to fuels or fires for particular purposes for improving the octane number
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/02Use of additives to fuels or fires for particular purposes for reducing smoke development
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1608Well defined compounds, e.g. hexane, benzene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/16Hydrocarbons
    • C10L1/1616Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/185Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852Ethers; Acetals; Ketals; Orthoesters

Abstract

The present invention provides a new gasoline fuel composition, having in combination an octane value (R+M)/2 of at least 85; an aromatics content less than 25 vol. %; and a water-soluble ethers content of less than 1 vol. %. The composition has a content of olefins, at least 10 % of which is formed by heavy olefins having a boiling point above +90 “C. In particular, the composition contains up to 40 % olefins, and it contains less than 6 vol.-% of light olefins having a boiling point below +90° C., and at least 1 vol.-% heavy branched olefins having a boiling point above +90° C. Reductions in emissions of pollutants can be obtained by introducing into an automotive engine an unleaded gasoline having a composition according to invention, combusting the unleaded gasoline in said engine; introducing at least some of the resultant engine exhaust emissions into the catalytic converter; and discharging emissions from the catalytic converter to the atmosphere.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0001]
  • The present invention relates to gasoline fuels. In particular, the present invention concerns gasoline fuels free from or having only a low content of water-soluble ethers. The present invention also relates to a method of reducing the emissions of one or more pollutants, selected from the group consisting of CO, NO[0002] x, particulates and hydrocarbons, from an automotive engine.
  • 2. Description of Related Art [0003]
  • Currently large amounts of water-soluble ethers (e.g. MTBE, methyl tert-butyl ether) are used by petroleum refiners as gasoline components for formulating gasoline products, which, upon combustion in automotive engines, will give rise to low exhaust emissions of harmful pollutants, such as carbon monoxide and nitrogen oxides. To mention an example, present-day Californian grade gasoline, abbreviated CARB II (California Phase II gasoline), contains about 12 vol.-% MTBE and it essentially meets the specifications set by the California Air Resources Board. It has an oxygen content of about 2%. However, MTBE is water-soluble and biologically very stable, and it may have a tendency to accumulate in groundwater. Thus, the use of water-soluble ethers, such as MTBE, as a component of gasoline fuels will have to be avoided in the future in California and alternative solutions should be found to provide clean-burning high-performance fuels for automotive engines. [0004]
  • SUMMARY OF THE INVENTION
  • It is an aim of the present invention to eliminate the disadvantages of the prior art and to provide a novel gasoline fuel, which is essentially free from water-soluble ethers while still meeting stringent exhaust emission limits. [0005]
  • It is another object of the invention to provide a method of reducing the emissions of an automotive engine of one or more pollutants selected from the group consisting of CO, NOx, particulates and hydrocarbons compared to combusting a CARB II fuel. [0006]
  • These and other objects of the invention and benefits associated therewith will become evident from the following detailed description of the invention. [0007]
  • The present invention is based on the finding that when gasoline fuels without a significant amount of water soluble ethers are produced by blending several hydrocarbon-containing streams together so as to formulate a gasoline product suitable for combustion in a gasoline spark-ignition internal combustion engine, reductions in the emissions of one or more pollutants selected from the group consisting of CO, NOx, particulates and hydrocarbons upon combustion of the gasoline product in such an engine system can be attained by controlling certain chemical and/or physical properties of said gasoline product. [0008]
  • It is well known that olefins, primarily light olefins and in particular tertiary olefins, contribute to the formation of ozone in the atmosphere. However, the relative ozone formation potential of heavy olefins, with a boiling point greater than about 90° C. (194° F.), is very low. [0009]
  • We have found that heavier olefins have a positive effect on the tail pipe emissions and, therefore, it is advantageous to control and minimize the amount of light olefins only in automotive gasoline. [0010]
  • According to the present invention, the content of light olefins, having a boiling point below +90° C. (194° F.), in particular below 85° C. (185° F.), should be less than about 10 vol.-%, preferably less than 6 vol.-% of the gasoline composition. These olefins are made up by C[0011] 2-C6 hydrocarbons. By contrast, the content of heavy olefins having a boiling point above +90° C., preferably above +95° C. (203° F.), can be more than 1 vol.-%, preferably 2 vol.-% or more, up to about 30 vol.-%. Suitable heavy olefins contain 8 carbon atoms or more and they are preferably branched. Particularly preferred examples include branched isoolefins containing 8 to 12 carbon atoms, such as trimethylpentenes (isooctenes), trimethylhexenes and trimethylheptenes.
  • In the fuel, the heavy olefins can used together with paraffines, in particular isoparaffines, such as isooctane, and with alcohols, such as ethanol or methanol. [0012]
  • Thus generally, the invention provides a gasoline fuel composition, having in combination [0013]
  • an octane value (R+M)/2 of at least 85; [0014]
  • an aromatics content less than 25 vol. %; and [0015]
  • a water-soluble ethers content of less than 1 vol. %. [0016]
  • The composition has a content of olefins, at least 10% of which is formed by heavy olefins having a boiling point above +90° C. In particular, the composition contains up to 40% olefins, and it contains less than 6 vol.-% of light olefins having a boiling point below +90° C., and at least 1 vol.-% heavy branched olefins having a boiling point above +90° C.”[0017]
  • According to an exemplifying embodiment, the present invention concerns an unleaded, clean-burning gasoline fuel with a low content of water-soluble ethers, suitable for combustion in a spark-ignition internal combustion engine and especially in a gasoline direct injection, lean-burning automotive engine having the following properties: [0018]
  • an octane value (R+M)/2 of at least 85; [0019]
  • an aromatics content less than 25 vol-%; [0020]
  • a water-soluble ethers content less than 1 vol-%; [0021]
  • a 10% D-86 distillation point no greater than +150° F. (65.6° C.); [0022]
  • a 50% D-86 distillation point no greater than +230° F. (110° C.); [0023]
  • a 90% D-86 distillation point no greater than +375° F. (190.6° C.); [0024]
  • Reid Vapor Pressure of less than 9.0 psi (62 kPa); [0025]
  • a light olefins content, with boiling point below +90° C., less than 6 vol-%; and [0026]
  • a combined content of trimethylpentenes, trimethylhexenes and trimethylheptenes greater than 1 vol. %. [0027]
  • Reductions in emissions of one or more pollutants selected from the group consisting of CO, NO[0028] x, particulates and hydrocarbons compared to combusting a CARB II fuel can be obtained by
  • a) introducing into said automotive engine an unleaded gasoline having a composition according to any of the above defined gasolines: [0029]
  • b) combusting the unleaded gasoline in said engine; [0030]
  • c) introducing at least some of the resultant engine exhaust emissions into the catalytic converter; and [0031]
  • d) discharging emissions from the catalytic converter to the atmosphere. [0032]
  • Considerable advantages are obtained by the present invention. As will appear from the results presented below, MTBE and similar water-soluble alkyl ethers can be replaced by an increased content of heavier olefins, in particular isoolefins, such as isooctene, in CARB gasoline, without any backsliding of exhaust gas quality. On the contrary, compared to an MTBE-containing fuel, when combusted in a spark ignition internal combustion engine, and particularly in a gasoline direct-injection, lean-burning automotive engine, the present fuels will produce a relatively low amount of gaseous pollutants, in particular one or more of NO[0033] x CO, particulates and unburned or incompletely burned hydrocarbons. Further, there would appear to be a reduction of fuel consumption.
  • Based on a study commissioned by the EU, there will be no ban on water-soluble alkyl ethers in gasoline in Europe in the foreseeable future, at least within the next 10 or 20 years. It should be pointed out that the present gasoline composition can also be easily converted for use with alkyl ethers by including a desired amount of an alkyl ether as an oxygenate component instead of an alcohol or in addition to that alcohol. In such gasolines, the total concentration of ether+alcohol can be up to 8 vol. % giving rise to an oxygen concentration of 1 to 3 vol. % Next, the invention will be examined more closely with the aid of the following detailed description with reference to the attached drawings. [0034]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows in the form of a bar chart the total hydrocarbon emissions of six different test cars for six different gasoline compositions; [0035]
  • FIG. 2 shows the corresponding bar chart of carbon monoxide emissions; [0036]
  • FIG. 3 shows the corresponding bar chart of nitrogen oxide (NOx) emissions; [0037]
  • FIG. 4 shows the corresponding bar chart of carbon dioxide emissions; [0038]
  • FIG. 5 shows the corresponding bar chart of combined HC and NOx emissions; [0039]
  • FIG. 6 shows the corresponding bar chart of particulate matter emissions; and [0040]
  • FIG. 7 shows the corresponding bar chart of gasoline consumption. [0041]
  • FIG. 8 shows in the form of bar chart the change (%) of the content of methane in exhaust gases compared to fuel RFG for two (E and F) cars of the set of test cars. [0042]
  • FIG. 9 shows the corresponding bar chart of 1,3-butadiene content of exhaust gases. [0043]
  • FIG. 10 shows the corresponding bar chart of benzene content of exhaust gases. [0044]
  • FIG. 11 shows the corresponding bar chart of BTEX compaunds content of exhaust gases. [0045]
  • FIG. 12 shows the corresponding bar chart of formaldehyde content of exhaust gases. [0046]
  • FIG. 13 shows the corresponding bar chart of acetaldehyde content of exhaust gases. [0047]
  • FIG. 14 shows content of polyaromatichydrocarbons (PAH14; EPA PAH) of the particulate matter of the exhaust gases from the two test cars (E and F). [0048]
  • FIG. 15 shows the amount of the semivolatile part of particulate matter above. [0049]
  • FIG. 16 shows the effect of particulate matter above on the AMES-mutagenicity (rev/mg). [0050]
  • FIG. 17 shows the effect of particulate matter above on the AMES-mutagenicity (krev/km). [0051]
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates to a low-emission, gasoline fuel composition, which is essentially free from water-soluble ethers typically used for increasing the octane number of the fuel and for improving the combustion properties thereof. The properties referred to above and in the following are determined by standard test methods outlined in Table 3. Thus, for example, distillation cuts are determined by ISO 3405 (corresponds to ASTM D86), and vapour pressure by EN 13016 [0052]
  • The ether content of the present fuel compositions is 1 vol.-% or less, preferably less than 0.6 vol.-%, in particular less than about 0.4 vol.-%. Thus, the gasoline composition is “essentially free from water-soluble ethers”. [0053]
  • Typically, the fuel has an octane value (R+M)/2 of at least 85, preferably at least 92, in particular at least 95. [0054]
  • The aromatics content is less than 25 vol. %. It has a total olefins content of more than about 7 vol.-%, typically less than about 40 vol.-%. A considerable part of the olefins are heavy olefins, such as C[0055] 7+olefins. When the total amount is about 7 vol. %, at least about 15% of the olefins are heavy, and when the total content is 20 to 30 vol.-%, the heavy olefins make up about 70 vol.-% or more.
  • It is preferred to limit the total concentration of olefins to about 20 vol.-%. [0056]
  • The preferred heavy olefins are isoolefins comprising 8 to 14 carbon atoms. In particular, the heavy olefins are selected from the group of branched octenes, nonenes and decenes. The following examples can be mentioned: trimethylpentenes, trimethylhexenes and trimethylheptenes. The combined content these compounds is 2 to 30 vol. %, and the isooctane, which represents a particularly preferred embodiment, typically stands for a content of 5 to 20 vol. %. [0057]
  • In addition to isoolefins, the present gasoline fuel composition can contain various amounts of paraffines, in particular isoparaffines. The latter are incorporated in amounts of 0.1 to 20 vol.-% preferably about 1 to 15 vol.-%. According to a preferred embodiment, the total content of isoolefins and isoparaffins is about 2 to 40 vol.-%. Isooctane is a typical isoparaffine, which can be used in up to 20 vol.-%. [0058]
  • The present fuel can also contain various oxygenates, such as alkanols (alcohols). As specific examples, ethanol and methanol can be mentioned. Ethanol-containing compositions contain ethanol in an amount of 0.01 to less than 6 vol.-%. The same concentration range is applicable to methanol. The alkanols can be derived from renewable sources. [0059]
  • By limiting the total concentration of olefins and the maximum concentration of light olefins, and further by using oxygenates it is possible to maintain good combustion properties of the gasoline while reducing emissions. [0060]
  • The concentration of oxygen in the fuel is generally about 0.1 to 5 mass %. Typically, the amount of alkanols is sufficient to provide the gasoline composition with an oxygen content of about 1 to 4 mass-%. [0061]
  • A fuel according to the present invention exhibits the following characteristics: [0062]
  • a 10% D-86 distillation point no greater than +150° F. (65.6° C.), in particular less than 140° F. (60° C.); [0063]
  • a 50% D-86 distillation point no greater than +230° F. (110° C. ), in particular less than 220° F. (104.4° C.); [0064]
  • a 90% D-86 distillation point no greater than +375° F. (190.6° C.), in particular less than 370° F. (187.8° C.); and [0065]
  • a Reid Vapor Pressure less than 9.0 psi (62 kPa), in particular less than 8.5 psi (58.6 kPa). [0066]
  • Based on experimental data, the particulate matter emissions were 50% lower than those of a conventional CARB II fuel, and the emissions of THC, NOx, CO and CO[0067] 2 were on the same level or lower as for CARB II fuels.
  • The experimental results shown below indicate that it is fully possible to provide gasoline compositions which are free from water-soluble and which, nevertheless, meet even stringent requirements for low emissions, by increasing the concentration of heavy olefins and by simultaneously reducing the concentration of light olefins. [0068]
  • The following, non-limiting example will elucidate the invention: [0069]
  • EXAMPLE
  • The composition of the gasoline is basically determined by the CARB specification. The present invention provides for a modification of that specification by the combined use of heavy olefins and isoparaffines, in particular isooctene and isooctane, optionally with oxygenates, in particular ethanol. [0070]
  • The exhaust emission tests were carried out with six different fuels. The fuels and their compositions are shown in Table 1 below: [0071]
    TABLE 1
    Compositions of Test Fuels
    TEST Aromatics
    FUELS Isooctane Isooctene NExTAME Ethanol MTBE Oxygen w-% Olefins vol-% vol-%
    RFG X X 2 15 35 ref
    CARB II X 2 5 25 ref
    CARB III IO X X 2 5 25
    CARB III IOE X X X 2 15 25
    IsoOkt X 5 25
    IsoOkte X X 15 25
  • In RFG, the concentration of TAME was 18 vol.-% and of MTBE 5 vol.-%. In CARB II, the concentration of MTBE was 12 vol.-%. [0072]
  • In the rest of the fuel compositions, the concentration of isooctane was 11 vol.-% and in CARB III IO and IsoOkte, the concentration of isooctane was 10 vol. %. [0073]
  • The properties of the isooctane and isooctene components, obtained from the Fortum NExOCTANE pilot plant in Porvoo, Finland, are given in Table 2. [0074]
    TABLE 2
    Properties of isooctane and isooctane components.
    Property Method Isooctane Isooctane
    RON ISO 5164 100.5 101.6
    MON ISO 5163 98.3 84.6
    Vapor pressure [kPa] 15.9 14
    Density [kg/m3] 701 729
    T10 distillation point [° C.] ASTM D86 98 102
    T50 distillation point [° C.] ASTM D86 100 105
    T90 distillation point [° C.] ASTM D86 119 117
    Olefin content, GC [% by volume] 0.5 97
    Aromatics content, GC [% by 0 0
    volume]
    Saturates, GC [% by volume] 99.5 0
  • [0075]
    TABLE 3
    Properties of test fuels
    CARB CARB CARB
    Code RFG II III IO III IOE IsoOkt IsoOkte
    Density ISO 12185 kg/m3 766 742 745 745 736 737
    at +15° C.
    Sulphur ASTM ppm 25 10 11 12 10 9
    D 3120
    Vapour EN 13016 kPa 62 59 61 63 60 61
    Pressure
    FIA-O ISO 3837
    Arom Vol-% 37 27 25 25 25 26
    Olef Vol-% 13 5 4 14 3 14
    Paraf + Naph Vol-% 38 58 65 55 72 60
    Oxygenates Vol-% 12 11 5 6 0 0
    Total 100 100 100 100 100 100
    C/H-ratio 6.93 6.49 6.45 6.56 6.50 6.59
    Content of NMR mass-% 12.70 13.50 13.60 13.50 14.00 13.70
    Hydrogen
    Benzene GC mass-% 0.70 0.37 0.35 0.39 0.34 0.37
    EtOH AED Vol-% 5.46 5.36 0.00 0.00
    TAME AED Vol-% 5.55 0.02 0.02 0.00 0.00 0.00
    MTBE AED Vol-% 4.48 11.09 0.02 0.03 0.03 0.04
    Other Vol-% 0.04 0.00 0.00 0.00
    Oxygenates
    Distillation ISO 3405
    IBP ° C. 33.4 29.3 35.4 32.9 28.5 33.0
    05 til-% ° C. 45.0 42.4 45.0 47.4 43.4 45.6
    10 til-% ° C. 54.0 50.5 51.8 52.4 53.6 54.2
    20 til-% ° C. 69.3 59.5 59.1 59.3 68.5 67.7
    30 til-% ° C. 81.6 68.0 66.6 67.2 81.6 79.8
    40 til-% ° C. 92.7 77.5 87.4 85.7 92.7 91.4
    50 til-% ° C. 103.0 88.7 101.0 98.9 101.3 100.4
    60 til-% ° C. 114.5 101.8 108.3 106.6 108.1 107.3
    70 til-% ° C. 126.7 114.8 116.4 114.4 115.2 114.5
    80 til-% ° C. 140.4 127.8 127.7 125.2 126.3 125.5
    90 til-% ° C. 155.3 147.5 148.5 146.3 147.7 146.8
    95 til-% ° C. 165.3 159.6 159.9 158.3 160.5 161.0
    FBP ° C. 196.6 189.7 190.1 187.6 189.6 190.7
  • Emissions were measured at 22° C. temperature for 6 vehicles using the European cycle for year 2000 (ECE+EUDC). Five of the vehicles have 4-cylinder, 16-valve engines equipped with multi point fuel injection (MPI) and a three-way catalytic converter (TWC). The swept volume of these vehicles A, B, C, D and F was form 1.3 liter to 2.0 liter. One vehicle (E) has the engine with six cylinder and the swept volume of 3.3 liters. Also this vehicle was equipped with multi point fuel injection (MPI) and a three-way catalytic converter (TWC [0076]
  • EMISSION TESTING—Exhaust emissions and fuel consumption of the vehicles were measured on a chassis dynamometer using the current European test cycle according to 70/220/EEC and its amendments. The test equipment used for exhaust dilution, collection of samples and analysis of samples are in compliance with the specifications of US EPA and directive 70/220/EEC and its amendments. [0077]
  • SAMPLING AND ANALYSES OF PARTICULATE AND SEMIVOLATILE MATTER—Particulates were collected at Fortum using a high capacity system and at the Technical Research Centre of Finland (VTT) using a similar system. The test procedure, sampling and analyses of particulate and semi-volatile matter was performed in a similar way as described by Kokko et al. [Kokko, J., Rantanen, L., Pentikäinen, J., Honkanen, T., Aakko, P., and Lappi, M., Reduced Particulate Emissions with Reformulated Gasoline, SAE Technical Paper 2000-01-2017, 2000]. Sampling and analytical procedures for the particulate and semi-volatile phases at both Fortum and VTT laboratories are briefly described in Lappi, M., Harmonisation of measuring methods of unregulated exhausts from passenger cars. Results of the Round-robin tests. Final report. VTT Energy Engine Technology. Mobile Research Program. Project 232T. March 1999. 50 p.+App. 119 p. [0078]
  • THC Emissions—The total hydrocarbon emissions are presented in FIG. 1. The THC emissions from the vehicles using a catalytic converter are with near all of the vehicles tested lower with the gasolines according to the present invention than with the other gasolines. [0079]
  • CO Emissions—Values presented in FIG. 2 show that, compared to CARB II, the carbon monoxide emissions are lower for five vehicles for CARB III IOE, whereas they are somewhat higher for ISO-OKTE. This confirms that the effect of oxygen in gasoline can be significant when reducing CO emissions especially in vehicles without closed loop fuel control systems. [0080]
  • NO[0081] x Emissions—Generally, gasoline with oxygenates slightly increases NOx emissions, and this was also found to be the case in this study, but lower for the gasolines according to the present invention compared to CARB II with all cars tested.
  • CO[0082] 2 Emissions and fuel consumption—The carbon dioxide emissions and gasoline consumption of the test vehicles are presented in FIGS. 4 and 7. CO2 emissions from all the gasolines are almost equal and the possible differences are within the confidence interval. All the differences fall within the confidence interval. Fuel consumption for the fuels with no oxygenates were lower than with oxygenates as expected.
  • Non-controlled emissions—With the two test cars (E and F) also the amount of so called non-controlled exhaust emissions were measured (FIGS. [0083] 8 to 13). From the figures can be seen that the results are more depending on the car measured than on the fuel tested. And no big differences cannot be seen.
  • PARTICULATE MASS EMISSIONS—The average particulate mass emissions at 22° C. with the two fuels and all vehicles are given in FIG. 6. Results are presented as average values derived from three or four tests on each fuel. Confidence intervals for these mean values are shown at the 95% level. With catalyst equipped vehicles the amount of particulate mass collected on the filters is very small compared to the weight of blank filters and thus the standard deviation of the results is rather high. Therefore the confidence intervals are quite large. Nevertheless, the gasolines according to the present invention have extremely low particulate mass emissions compared to all other gasolines, including CARB II. The toxic and mutagenic promerties of the particulate matter of the exhaust gases from the two test cars are represented in FIGS. [0084] 14 to 17. It can be seen that toxicity and the mutagenicity of the particulates with the fuel of the present invention were lower when compared to CARB II with all cars tested.
  • As the above test results, it is fully possible to replace MTBE in gasoline with heavy olefins without impairing the air quality of exhause gases. [0085]

Claims (12)

1. A gasoline fuel composition, having in combination
an octane value (R+M)/2 of at least 85;
an aromatics content less than 25 vol-%;
a water-soluble ethers content less than 1 vol-%;
a 10% D-86 distillation point no greater than +150° F. (65.6° C.);
a 50% D-86 distillation point no greater than +230° F. (110° C.);
a 90% D-86 distillation point no greater than +375° F. (190.6° C.);
Reid Vapor Pressure of less than 9.0 psi (62 kPa);
a content of light olefins, with a boiling point below +90° C., of less than 6 vol. %; and
a combined content of trimethylpentenes, trimethylhexenes and trimethylheptenes greater than 1 vol. %.
2. The gasoline fuel composition according to claim 1, having combined content of trimethylpentenes, trimethylhexenes and trimethylheptenes of 2 to 30 vol. %.
3. The gasoline fuel composition according to claim 2, having a content of isooctene in the range of 5 to 20 vol. %.
4. The gasoline fuel composition according to claim 1, further containing 0.1 to 20 vol. % of isoparaffines.
5. The gasoline fuel composition according to claim 4, wherein the total content of isoolefins and isoparaffins is 2 to 40 vol. %.
6. The gasoline fuel composition according to claim 1 wherein the total content of olefins is less than 20 vol. %.
7. The gasoline fuel composition according to claim 1, further having an ethanol content of 0.01 to less than 6 vol. %.
8. The gasoline fuel composition according to claim 1, wherein the concentration of oxygen is 0.1 to 5 mass %.
9. A gasoline fuel composition, having in combination
an octane value (R+M)/2 of at least 85;
an aromatics content less than 25 vol. %; and
a water-soluble ethers content of less than 1 vol. %;
wherein said composition has a content of olefins, at least 10% of which is formed by heavy olefins having a boiling point above +90° C.
10. A gasoline fuel composition, having in combination
an octane value (R+M)/2 of at least 85;
an aromatics content less than 25 vol. %; and
a water-soluble ethers content of less than 1 vol. %;
wherein said composition contains up to 40% olefins, and it contains less than 6 vol.-% of light olefins having a boiling point below +90° C., and at least 1 vol.-% heavy branched olefins having a boiling point above +90° C.
11. A method of reducing the emissions of an automotive engine of one or more pollutants selected from the group consisting of CO, NOx, particulates and hydrocarbons compared to combusting CARB 2 fuel, comprising
a) introducing into said automotive engine an unleaded gasoline according to claim 1 or 10
b) combusting the unleaded gasoline in said engine;
c) introducing at least some of the resultant engine exhaust emissions into the catalytic converter; and
d) discharging emissions from the catalytic converter to the atmosphere.
12. The method according to claim 11, wherein the gasoline further contains 0.01 to 6 vol. % ethanol.
US10/080,862 2001-08-15 2002-02-22 Clean-burning MTBE-free gasoline fuel Abandoned US20030094397A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US31241001P true 2001-08-15 2001-08-15
US10/080,862 US20030094397A1 (en) 2001-08-15 2002-02-22 Clean-burning MTBE-free gasoline fuel

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/080,862 US20030094397A1 (en) 2001-08-15 2002-02-22 Clean-burning MTBE-free gasoline fuel
EP20020748911 EP1417284A1 (en) 2001-08-15 2002-08-15 Clean-burning mtbe-free gasoline fuel
PCT/FI2002/000672 WO2003016438A1 (en) 2001-08-15 2002-08-15 Clean-burning mtbe-free gasoline fuel

Publications (1)

Publication Number Publication Date
US20030094397A1 true US20030094397A1 (en) 2003-05-22

Family

ID=26764043

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/080,862 Abandoned US20030094397A1 (en) 2001-08-15 2002-02-22 Clean-burning MTBE-free gasoline fuel

Country Status (3)

Country Link
US (1) US20030094397A1 (en)
EP (1) EP1417284A1 (en)
WO (1) WO2003016438A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279018A1 (en) * 2003-06-18 2005-12-22 Cracknell Roger F Gasoline composition
US20060260185A1 (en) * 2005-04-28 2006-11-23 Clean Diesel Technologies, Inc. Fuel Additive and Catalyst Treatment Process
US20150148572A1 (en) * 2013-11-27 2015-05-28 Saudi Arabian Oil Company Process for the Dimerization/Oligomerization of Mixed Butenes Over an Ion-Exchange Resin Catalyst
EP3502216A1 (en) * 2017-12-21 2019-06-26 Global Bioenergies Gasoline composition enabling reduced particulate emissions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019137896A1 (en) * 2018-01-10 2019-07-18 Shell Internationale Research Maatschappij B.V. A method for reducing particulate emissions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288393A (en) * 1990-12-13 1994-02-22 Union Oil Company Of California Gasoline fuel
US6132479A (en) * 1998-05-04 2000-10-17 Chevron U.S.A. Inc. Low emission, non-oxygenated fuel composition
US6241791B1 (en) * 1999-03-31 2001-06-05 Snamprogetti S.P.A. Liquid mixture suitable as gasoline
US20020014035A1 (en) * 1999-07-28 2002-02-07 Scott William R. Blending of summer gasoline containing ethanol
US6565617B2 (en) * 2000-08-24 2003-05-20 Shell Oil Company Gasoline composition
US20030150155A1 (en) * 2000-03-10 2003-08-14 Barbour Robert Howie Fuel composition
US20050000856A1 (en) * 2001-05-15 2005-01-06 Doherty Helen M. Reduced emissions transportation fuel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364997A (en) * 1992-10-05 1994-11-15 Mobil Oil Corporation Process for converting multi-branched heavy hydrocarbons to high octane gasoline
GB9922553D0 (en) * 1999-09-23 1999-11-24 Bp Oil Int Fuel compositions
GB2359094A (en) * 2000-02-14 2001-08-15 Exxonmobil Res & Eng Co Anti-foam fuel composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288393A (en) * 1990-12-13 1994-02-22 Union Oil Company Of California Gasoline fuel
US6132479A (en) * 1998-05-04 2000-10-17 Chevron U.S.A. Inc. Low emission, non-oxygenated fuel composition
US6241791B1 (en) * 1999-03-31 2001-06-05 Snamprogetti S.P.A. Liquid mixture suitable as gasoline
US20020014035A1 (en) * 1999-07-28 2002-02-07 Scott William R. Blending of summer gasoline containing ethanol
US20030150155A1 (en) * 2000-03-10 2003-08-14 Barbour Robert Howie Fuel composition
US6565617B2 (en) * 2000-08-24 2003-05-20 Shell Oil Company Gasoline composition
US20050000856A1 (en) * 2001-05-15 2005-01-06 Doherty Helen M. Reduced emissions transportation fuel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279018A1 (en) * 2003-06-18 2005-12-22 Cracknell Roger F Gasoline composition
AU2004249899B2 (en) * 2003-06-18 2008-08-07 Shell Internationale Research Maatschappij B.V. Gasoline composition
US7597724B2 (en) * 2003-06-18 2009-10-06 Shell Oil Company Gasoline composition
US20060260185A1 (en) * 2005-04-28 2006-11-23 Clean Diesel Technologies, Inc. Fuel Additive and Catalyst Treatment Process
US20150148572A1 (en) * 2013-11-27 2015-05-28 Saudi Arabian Oil Company Process for the Dimerization/Oligomerization of Mixed Butenes Over an Ion-Exchange Resin Catalyst
EP3502216A1 (en) * 2017-12-21 2019-06-26 Global Bioenergies Gasoline composition enabling reduced particulate emissions

Also Published As

Publication number Publication date
EP1417284A1 (en) 2004-05-12
WO2003016438A1 (en) 2003-02-27

Similar Documents

Publication Publication Date Title
Poulopoulos et al. Regulated and unregulated emissions from an internal combustion engine operating on ethanol-containing fuels
EP0748364B1 (en) Unleaded fuel compositions
US5308365A (en) Diesel fuel
DE69723558T2 (en) alternative fuel
CN1177914C (en) Method of reducing vapour pressure of ethanol-containing motor fuels for spark ignition combustion engine
AU717092B2 (en) Synthetic diesel fuel with reduced particulate matter emissions
CN101146896B (en) Mixed alcohol fuels for internal combustion engines, furnaces, boilers, kilns and gasifiers
ES2214549T3 (en) Synthetic diesel fuel and process for their production.
Hsieh et al. Engine performance and pollutant emission of an SI engine using ethanol–gasoline blended fuels
US6858048B1 (en) Fuels for internal combustion engines
EP1027409B2 (en) Blended compression-ignition fuel containing light synthetic crude and blending stock
Wu et al. The influence of air–fuel ratio on engine performance and pollutant emission of an SI engine using ethanol–gasoline-blended fuels
EP0507510A1 (en) Reduction of NOx emissions from gasoline engines
Rakopoulos et al. Operational and environmental evaluation of diesel engines burning oxygen-enriched intake air or oxygen-enriched fuels: a review
US5906664A (en) Fuels for diesel engines
US20040123516A1 (en) Method for making a fuel for a modified spark ignition combustion engine, a fuel for a modified spark ignition combustion engine and a fuel additive for a conventional spark ignition combustion engine
EP1359207B1 (en) Fuel composition
US20040123518A1 (en) Alcohol enhanced alternative fuels
US5599357A (en) Method of operating a refinery to reduce atmospheric pollution
CA2197201C (en) Diesel fuel composition
De Menezes et al. Addition of an azeotropic ETBE/ethanol mixture in eurosuper-type gasolines
JP4450618B2 (en) Ethanol-containing gasoline
EP0905217A1 (en) Unleaded gasoline for direct injection gasoline engine
USH1305H (en) Reformulated gasolines and methods of producing reformulated gasolines
JP3782139B2 (en) Unleaded petrol

Legal Events

Date Code Title Description
AS Assignment

Owner name: FORTUM OYJ, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IGNATIUS, JYRKI;JAKKULA, JUHA;NASI, RISTO;AND OTHERS;REEL/FRAME:012999/0776;SIGNING DATES FROM 20020515 TO 20020516

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION