CN111556890A - Method for reducing particulate emissions - Google Patents

Method for reducing particulate emissions Download PDF

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Publication number
CN111556890A
CN111556890A CN201980007521.0A CN201980007521A CN111556890A CN 111556890 A CN111556890 A CN 111556890A CN 201980007521 A CN201980007521 A CN 201980007521A CN 111556890 A CN111556890 A CN 111556890A
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Prior art keywords
base fuel
gasoline composition
particulate emissions
fuel
gasoline
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Pending
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CN201980007521.0A
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Chinese (zh)
Inventor
R·F·克拉克内尔
A·A·阿拉迪
V·佩利切亚里
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN111556890A publication Critical patent/CN111556890A/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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons 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
    • C10L1/023—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
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Abstract

A method for reducing particulate emissions from a direct injection spark ignition engine, wherein the method comprises fuelling the engine with a gasoline composition, wherein the gasoline composition comprises a hydrocarbon base fuel comprising not more than 5% v, based on the base fuel, of aromatic hydrocarbons having at least 9 carbon atoms, a T90 of up to 150 ℃ and a final boiling point of not more than 190 ℃.

Description

Method for reducing particulate emissions
Technical Field
The present invention relates to a method for reducing particulate emissions from a direct injection spark ignition engine.
Background
There is an increasing concern about the environmental impact of particulate emissions from spark-ignition combustion engines, particularly direct injection spark-ignition engines. This has led to an increasing demand for motor vehicles which can be operated with reduced particle emissions.
Hydrocarbon fuels currently being developed for spark-ignition combustion engines may not be optimized or may actually be disadvantageous for direct injection spark-ignition engines, particularly when particulate emission levels are referenced. It is therefore desirable to find ways to reduce particulate emissions from operating a direct injection spark ignition engine.
WO2004/113476 discloses a gasoline composition meeting certain parameters for use as fuel in a spark ignition engine resulting in improved stability of the engine crankcase lubricant. However, there is no mention in this document of the use of such fuels for reducing particulate emissions in a direct injection spark ignition engine.
Disclosure of Invention
According to the present invention there is provided a method for reducing particulate emissions from a direct injection spark ignition engine, wherein the method comprises fuelling the engine with a gasoline composition, wherein the gasoline composition comprises a hydrocarbon base fuel comprising no more than 5% v, based on the base fuel, of aromatic hydrocarbons having at least 9 carbon atoms, a T90 of up to 150 ℃ and a final boiling point of no more than 190 ℃.
According to the present invention there is further provided the use of a gasoline composition for reducing particulate emissions from a direct injection spark ignition engine, wherein the gasoline composition comprises a hydrocarbon base fuel comprising not more than 5% v, based on the base fuel, of aromatic hydrocarbons having at least 9 carbon atoms, a T90 below 150 ℃ and a final boiling point of not more than 190 ℃.
It has been surprisingly found that by selecting a gasoline composition that meets certain parameters, particulate emissions from a direct injection spark ignition engine can be reduced.
Detailed Description
The low C9+ aromatics content, along with a T90 of less than 150 ℃ and a final boiling point of no more than 190 ℃, is considered a key parameter for reducing particulate emissions from a direct injection spark ignition internal combustion engine fueled by the gasoline composition of the present invention.
By "not more than 5% v of aromatics having at least 9 carbon atoms" is meant that the hydrocarbon base fuel contains aromatics having 9 or more carbon atoms in the range of 0 to 5% v, respectively, based on the amount of the base fuel.
The use and method of the present invention may be used to achieve any degree of reduction in particulate emissions from a direct injection spark ignition engine, including reduction to 0 (i.e. elimination of particulate emissions). Which may be used for the purpose of achieving a desired target level of particulate emissions. The methods and uses herein preferably achieve 5% reduction or greater in particulate emissions from a direct injection spark ignition engine, more preferably 10% reduction or greater in particulate emissions from a direct injection spark ignition engine, even more preferably 15% reduction or greater in particulate emissions from a direct injection spark ignition engine, and particularly preferably 30% reduction or greater in particulate emissions from a direct injection spark ignition engine, as compared to using a gasoline fuel composition having a final boiling point of greater than 190 ℃, having a T90 of 150 ℃ or greater than 150 ℃, and comprising greater than 5 v% of an aromatic hydrocarbon having 9 or more carbon atoms.
Any suitable method may be used herein to measure particulate emissions from a direct injection spark ignition engine. One example of a suitable method for measuring particulate emissions can be found in the following SAE paper: SAE stages 2010-01-2115, 10/25/2010, which measures the reduction in particulate emissions by a reduction in the PM index of the gasoline composition. The gasoline composition suitable for use in the present invention preferably has a PM index of 1.0 or less, more preferably 0.95 or less, even more preferably 0.9 or less, measured according to the test method disclosed in SAE 2010-01-2115.
Gasoline contains a mixture of hydrocarbons whose optimum boiling range and distillation curve vary according to the climate and season of the year. The hydrocarbons in gasoline as defined above may be conveniently derived in known manner from straight run gasoline, synthetically produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbons, hydrocracked petroleum fractions or catalytically reformed hydrocarbons and mixtures of these. Oxygenates, whether fossil or bio-derived, can be incorporated into gasoline and comprise alcohols (e.g., methanol, ethanol, isopropanol, tert-butanol and isobutanol) and ethers, preferably ethers containing 5 or more carbon atoms per molecule, such as methyl tert-butyl ether (MTBE) or ethyl tert-butyl ether (ETBE). The amount of oxygenate present in the fuel composition depends on the current fuel specifications for the oxygenate type. For example, the EN228 specification defines the maximum oxygen content as 3.73% oxygen by mass, and so the level of oxygenate must be adjusted to meet this specification.
It is preferred to avoid the inclusion of tert-butanol or MTBE. Accordingly, preferred gasoline compositions of the present invention contain 0 to 10% by volume of at least one oxygenate selected from the group consisting of methanol, ethanol, isopropanol, and isobutanol.
Theoretical modeling has shown that the inclusion of ethanol in the gasoline composition of the present invention will further enhance the stability of engine lubricants, particularly under cooler engine operating conditions. Thus, it is preferred that the gasoline composition of the present invention contains up to 10% ethanol by volume, preferably 2 to 10% v, more preferably 4 to 10% v, for example 5 to 10% v ethanol.
Other oxygenates that may be included in the gasoline compositions herein include ethanol and CO2Diethyl carbonate (DEC), esters (e.g., ethyl acetate), and ketones (e.g., methyl ethyl ketone) produced by catalysis.
Oxygenates may help reduce PN emissions by chemical means.
The gasoline composition according to the invention is advantageously lead-free (lead-free) and this may be required by law. Where warranted, lead-free explosion-proof compounds and/or valve seat recession protector compounds (e.g., known potassium, sodium or phosphorus compounds) may be present.
Octane levels can be defined by RON, MON or explosion proof index (Aki) ((RON + MON)/2). If RON is specified, it will typically be greater than 92. If an explosion protection index is specified, it will typically be higher than 85.
Modern gasoline is essentially a low sulphur fuel, for example containing less than 200ppmw sulphur, preferably no more than 50ppmw sulphur.
As will be readily understood by a person skilled in the art, a hydrocarbon base fuel as defined above may conveniently be produced in a known manner by blending suitable hydrocarbon (e.g. refinery) streams to meet the defined parameters. The olefin content can be increased by including an olefin-rich refinery stream in any relative proportion and/or by adding a synthesis component (e.g., diisobutylene).
Diisobutylene, also known as 2,4, 4-trimethyl-1-pentene (Sigma Aldrich Fine Chemicals, usa), is typically a mixture of isomers (2,4, 4-trimethyl-1-pentene and 2,4, 4-trimethyl-2-pentene) prepared by heating the sulfuric acid extract of isobutylene from the butene isomer separation process to about 90 ℃. The yield was typically 90% with 80% dimer and 20% trimer mixed as described in cocker-ostmo (Kirk-Othmer) encyclopedia of chemical technology, 4 th edition, volume 4, page 725.
The gasoline composition as defined above may comprise one or more additives such as antioxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and synthetic or mineral oil carrier fluids in various ways. Examples of suitable such additives are generally described in U.S. Pat. No.5,855,629 and DE-A-19955651.
The additive components may be added to gasoline individually or may also be blended with one or more diluents to form an additive concentrate and added together to the base fuel.
Preferred gasoline compositions for use in the process of the present invention include one or more antioxidants to improve the oxidative stability of the gasoline composition. Any antioxidant additive suitable for use in gasoline compositions may be used herein. Preferred antioxidants for use herein are hindered phenols such as Butylated Hydroxytoluene (BHT). Preferably, the gasoline composition comprises from 10ppmw to 100ppmw of antioxidant.
The high octane components that may be biologically derived and suitable for use herein that are free of oxygen include isobutylene or isooctenes, isooctanes, trimethylbutanes, and isoamylenes. These high octane oxygen-free compounds may help reduce PN emissions through ignition and combustion optimization.
Preferred gasoline compositions for use in the process of the present invention have one or more of the following characteristics: -
(i) The hydrocarbon base fuel contains at least 10% v olefins,
(ii) the hydrocarbon base fuel contains at least 12% v olefins,
(iii) the hydrocarbon base fuel contains at least 13% v olefins,
(iv) the hydrocarbon base fuel contains up to 20% v olefins,
(v) the hydrocarbon base fuel contains up to 18% v olefins,
(vi) the base fuel has an Initial Boiling Point (IBP) of at least 28 c,
(vii) the base fuel has an IBP of at least 30 c,
(viii) the base fuel has an IBP up to 42 c,
(ix) the base fuel has an IBP up to 40 c,
(x) The base fuel has a T of at least 42 DEG C10，
(xi) The base fuel has a T of at least 45 DEG C10，
(xii) The base fuel has a T of at least 46 DEG C10，
(xiii) The base fuel has a T of up to 58 DEG C10，
(xiv) The base fuel has a T of up to 57 DEG C10，
(xv) The base fuel has a T of up to 56 DEG C10，
(xvi) The base fuel has a T of at least 80 DEG C10，
(xvii) The base fuel has a T of at least 82 DEG C10，
(xviii) The base fuel has a T of at least 83 DEG C10，
(xix) The base fuel has a T of up to 105 DEG C10，
(xx) The base fuel has a T of up to 104 DEG C10，
(xxi) The base fuel has a T of up to 103 DEG C10，
(xxii) Basic fuelThe material has a T of at least 135 DEG C90，
(xxiii) The base fuel has a T of at least 140 DEG C90，
(xxiv) The base fuel has a T of at least 142 DEG C90，
(xxv) The base fuel has a T of up to 150 DEG C90，
(xxvi) The base fuel has a T of up to 145 DEG C90，
(xxvii) The base fuel has a T of up to 143 DEG C90，
(xxviii) The base fuel has an FBP of no greater than 190 c,
(xxix) The base fuel has an FBP of no greater than 185 c,
(xxx) The base fuel has an FBP of no greater than 180 c,
(xxxi) The base fuel has an FBP of no greater than 175 c,
(xxxii) The base fuel has an FBP of no greater than 172 c,
(xxxiii) The base fuel has an FBP of at least 165 ℃, and
(xxxiv) The base fuel has an FBP of at least 168 ℃.
Examples of preferred combinations of the above features include (i) and (iv); (ii) and (v); (iii) and (v); (vi) (viii), (x), (xii), (xvi), (xix), (xxii), (xxv), and (xxix); (vii) (ix), (xi), (xiv), (xvii), (xx), (xxiii), (xxv), and (xxx); and (vii), (ix), (xii), (xv), (xviii), (xxi), (xxiv), (xxvii), (xxxiii), and (xxxiv).
In addition to reducing particulate emissions in direct injection spark ignition engines, the use of the gasoline compositions described herein may provide one of a number of benefits. These benefits include reduced frequency of oil changes, reduced wear on the engine (e.g., wear on engine bearings), reduced wear on engine components (e.g., wear on camshafts and piston cranks), improved acceleration performance, increased maximum power output, and/or improved fuel economy.
The invention will be understood from the illustrative examples that follow, wherein temperatures are in degrees celsius and parts, percentages and ratios are by volume unless otherwise indicated. Those skilled in the art will readily appreciate that various fuels are prepared in known manners from known refinery streams and, therefore, can be readily reproduced based on knowledge of given composition parameters.
In an example, a particulate matter emissions test for a gasoline composition in a direct injection spark ignition engine fueled by a test fuel was achieved using the following steps.
Examples of the invention
The fuel compositions of examples 1 to 4 are shown in table 2 below. Each of these fuel compositions was prepared from a gasoline base fuel having the characteristics listed in table 1 below, and for each example, the v% of heavy aromatics (aromatics having at least 10 carbon atoms) was adjusted to contain an amount of heavy aromatics (C9+) as specified in table 2 below. Thus, example 1 contained 0% v of heavy aromatics, example 2 contained 4% v of heavy aromatics, example 3 contained 8% v of heavy aromatics, and example 4 contained 12% v of heavy aromatics.
TABLE 1 (characteristics of base fuels)
IBP(℃) 31.9
T10(℃) 47.3
T50(℃) 102.0
T90(℃) 142.7
FBP(℃) 179.3
RVP(kPa) 65.1
RON 95.3
MON 82.9
Aki((RON+MON)/2) 89.1
Sensitivity (RON-MON) 12.43
Alkane (% v) 49.7
Olefin (% v) 14.3
Aromatic hydrocarbons (% v) 32.7
PM index 0.81
C9 aromatic hydrocarbons (% v) 2.65
C10 aromatic hydrocarbons (% v) 0.26
C11 aromatic hydrocarbons (% v) 0.00
C12 aromatic hydrocarbons (% v) 0
The fuel compositions in Table 2 were subjected to the particulate matter emissions test described in SAE paper, 2010-01-2115 to measure their PN index. The results are shown in table 2 below.
TABLE 2
Example (c): 1 2 3 4
% v weight (C9+) aromatic hydrocarbons 0％v 4％v 8％v 12％v
IBP(℃)) 32.9 32.65 32.95 33.27
T10(℃) 49.0 48.2 49.32 50.50
T50(℃) 100.1 102.5 106.11 109.90
T90(℃) 134.7 144.1 148.52 153.88
FBP 152.9 189.6 201.90 211.72
RVP(kPa) 66.15 68.58 66.51 64.42
RON 96.7 96.0 96.51 97.12
MON 82.8 82.7 83.08 83.49
Aki 89.8 89.3 89.8 90.3
Sensitivity of the probe 13.9 13.3 13.4 13.6
Alkane (% v) 44.9 44.5 42.66 40.81
Olefin (% v) 20.3 20.2 19.31 18.48
Aromatic hydrocarbons (% v) 32.50 33.07 35.86 38.63
PM index 0.75 0.89 1.08 1.315
C9 aromatic hydrocarbons (% v) 0 3.00 5.98 8.44
C10 aromatic hydrocarbons (% v) 0 0.70 1.25 2.30
C11 aromatic hydrocarbons (% v) 0 0
C12 aromatic hydrocarbons (% v) 0 0.30 0.77 1.24
C9+ aromatic hydrocarbons (% v) 0 4.00 8.00 11.98
Discussion of the invention
As can be seen from the results in table 2 above, a gasoline composition having a hydrocarbon base fuel comprising not more than 5% v, based on the base fuel, of aromatics having at least 9 carbon atoms, a T90 below 150 ℃ and a final boiling point no higher than 190 ℃, can reduce particulate emissions to a greater extent (as measured by a reduction in PM index).

Claims (11)

1. A method for reducing particulate emissions from a direct injection spark ignition engine, wherein the method comprises fuelling the engine with a gasoline composition, wherein the gasoline composition comprises a hydrocarbon base fuel comprising no more than 5% v, based on the base fuel, of aromatic hydrocarbons having at least 9 carbon atoms, a T90 of up to 150 ℃ and a final boiling point of no more than 190 ℃.
2. The method of claim 1, wherein the hydrocarbon base fuel has a final boiling point of no greater than 180 ℃.
3. The method of claim 1 or 2, wherein said reduction in particulate emissions is measured by a reduction in the PM index (stage 2010-01-2115) of said gasoline composition.
4. The method of any one of claims 1 to 3 wherein the PM index of the gasoline composition is 1.0 or less.
5. The method of any one of claims 1 to 4 wherein the gasoline composition contains 0 to 10% v of at least one oxygenate selected from the group consisting of methanol, ethanol, isopropanol, and isobutanol, and diethyl carbonate.
6. The method of any one of claims 1 to 5, wherein the hydrocarbon base fuel contains 10 to 20% v olefins.
7. The method of any one of claims 1 to 6, wherein the hydrocarbon base fuel contains 12 to 18% v olefins.
8. The method of any one of claims 1 to 7, wherein the hydrocarbon base fuel contains no more than 5% v, based on the base fuel, of olefins having at least 10 carbon atoms.
9. The method of any one of claims 1 to 8, wherein the base fuel has an initial boiling point in the range of 30 to 40 ℃, a T10 in the range of 45 to 57 ℃, a T50 in the range of 82 to 104 ℃, a T90 in the range of 140 to 150 ℃.
10. The method of any one of claims 1 to 9, wherein the fuel composition comprises one or more antioxidants.
11. Use of a gasoline composition for reducing particulate emissions from a direct injection spark ignition engine, wherein the gasoline composition comprises a hydrocarbon base fuel comprising no more than 5% v, based on the base fuel, of aromatic hydrocarbons having at least 9 carbon atoms, a T90 of up to 150 ℃ and a final boiling point of no more than 190 ℃.
CN201980007521.0A 2018-01-10 2019-01-08 Method for reducing particulate emissions Pending CN111556890A (en)

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WO2002077126A1 (en) * 2001-03-27 2002-10-03 Exxonmobil Research And Engineering Company Tuning fuel composition for driving cycle conditions in spark ignition engines
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