US20080295395A1 - Additives for Reduction of Exhaust Emissions From Compression Ignition Engines - Google Patents
Additives for Reduction of Exhaust Emissions From Compression Ignition Engines Download PDFInfo
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- US20080295395A1 US20080295395A1 US12/128,918 US12891808A US2008295395A1 US 20080295395 A1 US20080295395 A1 US 20080295395A1 US 12891808 A US12891808 A US 12891808A US 2008295395 A1 US2008295395 A1 US 2008295395A1
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- fuel
- nitrate
- emissions
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- additive composition
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- 239000000654 additive Substances 0.000 title claims abstract description 48
- 238000007906 compression Methods 0.000 title abstract description 5
- 230000006835 compression Effects 0.000 title abstract description 5
- 230000009467 reduction Effects 0.000 title description 11
- 239000000446 fuel Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 63
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000013618 particulate matter Substances 0.000 claims abstract description 38
- -1 polypropylene Polymers 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 25
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 23
- 229920001519 homopolymer Polymers 0.000 claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 239000004743 Polypropylene Substances 0.000 claims abstract description 12
- 229920001155 polypropylene Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 16
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- NTHGIYFSMNNHSC-UHFFFAOYSA-N 3-methylbutyl nitrate Chemical compound CC(C)CCO[N+]([O-])=O NTHGIYFSMNNHSC-UHFFFAOYSA-N 0.000 claims description 4
- MSFXTEGGONNIJM-UHFFFAOYSA-N 4-methylpentyl nitrate Chemical compound CC(C)CCCO[N+]([O-])=O MSFXTEGGONNIJM-UHFFFAOYSA-N 0.000 claims description 4
- HLYOOCIMLHNMOG-UHFFFAOYSA-N cyclohexyl nitrate Chemical compound [O-][N+](=O)OC1CCCCC1 HLYOOCIMLHNMOG-UHFFFAOYSA-N 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- PAWHIGFHUHHWLN-UHFFFAOYSA-N dodecyl nitrate Chemical compound CCCCCCCCCCCCO[N+]([O-])=O PAWHIGFHUHHWLN-UHFFFAOYSA-N 0.000 claims description 4
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000003849 aromatic solvent Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000002816 fuel additive Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical group COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004679 ONO2 Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical group OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
-
- 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
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
-
- 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
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- 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
- C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
-
- 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
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
- C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
Definitions
- the present invention relates to additives for distillate fuels, and more particularly relates, in one embodiment to reducing exhaust emissions for hydro-carbon fuels using chemical additives.
- exhaust emissions from compression ignition (e.g. internal combustion) engines.
- These exhaust emissions are the products of burning the fuel in the engine, emitted from an exhaust system.
- the major emissions include hydrocarbons, which are unburned or partially burned fuels, nitrogen oxides (generally abbreviated NOx) which are generated when nitrogen in the air reacts with oxygen under the high temperature and pressure conditions inside the engine, carbon monoxide (CO) which is a product of incomplete combustion, and carbon dioxide (CO 2 ) which is a product of the complete combustion of hydrocarbons.
- NOx nitrogen oxides
- CO carbon monoxide
- CO 2 carbon dioxide
- Additives to fuels are known to reduce undesirable emissions.
- fuel additives that claim to lower emissions, such as particulate matter, unburnt hydrocarbon, and NOx.
- organo-metallic and totally organic formulations have been proposed and tried.
- diverse mechanisms have been proposed for their effectiveness.
- compositions for reducing the emissions of distillate fuels that includes a homopolymer such as polyisobutylene (PIB), polypropylene (PP), and/or a hyperbranched polymer.
- PIB polyisobutylene
- PP polypropylene
- hyperbranched polymer a homopolymer
- PIB polyisobutylene
- PP polypropylene
- a hyperbranched polymer a homopolymer
- alkyl nitrate such as 2-ethyhexylnitrate (2EHN)
- peroxide such as hydrogen peroxide
- distillate fuels such as diesel fuels, gasoline, jet fuels, or kerosene, having reduced emissions, that contains an effective amount of a composition to reduce emissions of a homopolymer that may be polyisobutylene, polypropylene, and/or a hyperbranched polymer, and optionally an alkyl nitrate and/or a peroxide.
- Also provided in another non-limiting embodiment are methods for reducing emissions of a distillate fuel by adding to the fuel an effective amount of a composition that includes a homopolymer that may be polyisobutylene, polypropylene, and/or a hyperbranched polymer, and optionally an alkyl nitrate and/or a peroxide.
- a composition that includes a homopolymer that may be polyisobutylene, polypropylene, and/or a hyperbranched polymer, and optionally an alkyl nitrate and/or a peroxide.
- FIG. 1 is a graph of NOx emissions in a distillate fuel showing NOx reduction measured as % as a function of total concentration of the additives herein;
- FIG. 2 is a graph of particulate matter emissions measured as a function of the total concentration of the additives for the fuels of FIG. 1 ;
- FIG. 3 is another graph of NOx emissions in a distillate fuel showing NOx reduction measured as % as a function of total concentration of an additive composition containing 10% hyperbranched polyalpha-olefin (HPAO) and 70% 2-ethylhexyl nitrate (EHN), the balance being solvent; and
- HPAO hyperbranched polyalpha-olefin
- EHN 2-ethylhexyl nitrate
- FIG. 4 is a graph of particulate emissions (PM) in a distillate fuel showing NOx reduction measured as % as a function of total concentration of an additive composition containing 10% hyperbranched polyalpha-olefin (HPAO) and 70% 2-ethylhexyl nitrate (EHN), the balance being solvent.
- HPAO hyperbranched polyalpha-olefin
- EHN 2-ethylhexyl nitrate
- the methods and compositions herein relate to reducing the amount of exhaust emissions resulting from the combustion of hydrocarbon fuels in compression ignition engines such as internal combustion engines.
- the additives reduce NOx emissions and/or particulate matter.
- the methods and compositions herein concern a fuel additive formulation that includes a polymer.
- Suitable polymers are homopolymers including, but not necessarily limited to, polyisobutylene, polypropylene, hyperbranched polymers, and in particular hyperbranched polyalpha-olefins (PAO), and the like.
- the hyperbranched polyalpha-olefins may be hyperbranched polymers of C4-C30 alpha-olefins, where the alpha-olefins may be acid- or alcohol-functionalized, and mixtures and derivatives thereof.
- the polymer presence lowers NOx and in many embodiments also lowers particulate matter (PM).
- the additive composition herein may also optionally contain a component that may be an alkyl nitrate and/or a peroxide.
- Suitable alkyl nitrates include, but are not necessarily limited to, 2-ethylhexyl nitrate (2EHN), CH 3 (CH 2 ) 3 CH(C 2 H 5 )CH 2 ONO 2 , iso-propyl nitrate, iso-amylnitrate, iso-hexylnitrate, cyclohexyl nitrate, dodecyl nitrate, diglycol nitrate and tetraglycol nitrate and the like. Ether nitrates and fatty acid nitrates may also be useful.
- the alkyl nitrate may function to primarily lower the NOx emissions although reduction in PM may also be expected. Alternatively, NOx emissions may be lowered by the compositions herein without appreciably raising PM levels, which would also be an advantage and an improvement
- the additive composition may also optionally include a peroxide, in place of or in addition to the alkyl nitrate.
- Suitable peroxides include, but are not necessarily limited to, hydrogen peroxide, di-tertiary butyl peroxide, and benzoyl peroxide and the like. Further, some synergism has been found between the homopolymer and the alkyl nitrate and/or peroxide.
- Known cetane boosters for use in distillate fuels include 2-ethylhexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, and mixtures thereof.
- Conventional, known ignition accelerators include hydrogen peroxide, benzoyl peroxide, di-tert-butyl peroxide, and the like.
- hyperbranched polyalpha-olefins polymers prepared by polymerizing hydrocarbons under free radical conditions at low pressures.
- the polymers are unique in that although hydrocarbon polymers generally have higher molecular weight, greater viscosity and greater hardness than the starting hydro-carbon these polymers generally have higher melting points and congealing points than the starting hydrocarbons.
- the hydrocarbons employed are primarily alpha-olefins of the formula RCH ⁇ CH 2 but also include alpha-olefins having vinylidene structures, internal olefins and saturates, where R is an alkyl or alkylene group, including those having vinylidene structures.
- Suitable hyperbranched polyalpha-olefins are those made according to the methods described in U.S. Pat. Nos. 4,060,569; 4,239,546 and 6,776,808, all incorporated by reference herein in their entirety.
- the hyperbranched polyalpha-olefins are considered homopolymers herein under the classic definition because they are made from a single monomer.
- Suitable hyperbranched polyalpha-olefins herein may have a number average molecular weight (M n ) of from about 100 to about 275,000, alternatively a lower threshold of about 150 and independently an upper threshold of about 250,000, and in another non-limiting embodiment from about 200 independently up to about 175,000, or even up to about 125,000
- M n number average molecular weight
- polymers that may also be useful in the additive compositions herein include, but are not necessarily limited to, isotactic polypropylene (such as ones having a weight average molecular weight in the range of about 2000) or higher molecular weight hyperbranched polymer products than those described above. Polymer alone without the 2EHN may be useful.
- distillate fuels include, but are not necessarily limited to diesel fuel, kerosene, gasoline, jet fuel, and the like. It will be appreciated that distillate fuels include blends of conventional hydrocarbons meant by these terms with oxygenates, e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, such as MTBE (methyl-tert-butyl ether), or that may be used in the future.
- oxygenates e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, such as MTBE (methyl-tert-butyl ether), or that may be used in the future.
- MTBE methyl-tert-butyl ether
- distillate fuels include low sulfur fuels, which are defined as having a sulfur content of 0.2% by weight or less, and in another non-limiting embodiment as having a sulfur content of about 0.0015 wt. % or less—such as the so-called “ultra low sulfur” fuels.
- Particularly preferred hydrocarbon fuels herein are diesel and kerosene. It is expected that a more conventional diesel fuel (i.e. with an aromatic content of >28%) treated with the additive composition herein will be equivalent in emissions to a Texas Low Emissions Diesel (TxLED) fuel with ⁇ 10% aromatic content.
- TxLED Texas Low Emissions Diesel
- the composition for improving the emissions of distillate fuels is a mixture or blend of 2EHN (or a peroxide component) and at least one of the homopolymers.
- the homopolymer is present in the fuel in the range of about 20 to about 2500 ppm, in one non limiting embodiment from about 20 independently up to about 300 ppm; alternatively from about 20 independently up to about 150 ppm.
- the alkyl nitrate, particularly 2EHN may be present in the fuel in the range of about 100 to about 3000 ppm, alternatively from about 500, independently up to about 1500 ppm.
- the volume ratio of homopolymer to the component ranges from about 1:1 to about 1:100, and alternatively the volume ratio of homopolymer to the component ranges from about 1:2 to about 1:10; and in one particularly suitable ratio, about 1:7.
- a solvent may be advantageously used in the compositions herein, where the solvent may be aromatic solvents and pure paraffinic solvents. Aromatic solvents are particularly preferred.
- the proportion of solvent in the total fuel additive composition may range from about 0 to 90 weight %; in another non-restrictive embodiment, the solvent may range from a lower threshold of about 15 wt % independently to an upper threshold of 45 wt %.
- the use of a solvent is optional. In some non-limiting embodiments, no solvent is used or desired. A non-restrictive example would be 87.5% 2EHN and 12.5% HPAO with no solvent (a 7:1 ratio of active components).
- suitable solvents include, but are not limited to paraffins and cycloparaffins, aromatic naphtha, kerosene, diesel, gasoline, xylene, toluene, alcohols (e.g. 2-ethylhexanol), and the like.
- compositions herein also encompass distillate fuels containing the additive compositions described herein, as well as methods of improving the emissions properties of distillate fuels using the additive compositions described herein.
- distillate fuels in non-limiting embodiments may include, but are not necessarily limited to detergents, pour point depressants, cetane improvers, lubricity additives, dehazers, cold operability additives, conductivity additives, biocides, dyes, and mixtures thereof.
- Particularly useful components may include condensation reaction products of aldehydes and amines which are useful as antioxidants and are effective to lower PM and unburnt hydrocarbon (HC).
- HC unburnt hydrocarbon
- a specific non-limiting example is the condensation reaction product between formaldehyde and di-n-butylamine.
- water is explicitly absent from the additive composition.
- Additive compositions expected to be useful herein include, but are not necessarily limited to the following outlined in Table I:
- Probes for background gas measurement were connected downstream of the dilution air filter pack, but upstream of the mixing section.
- the dilution system was equipped with pressure and temperature sensors at various locations in order to obtain all necessary information required by the U.S. Code of Federal Regulation (40 CFR, Part 86, Subpart N).
- FIG. 1 depicts the NOx mitigation that is achieved with various formulations of HPAO and PIB, alone and in combination with EHN in a compression ignition fuel.
- the y-axis indicates the percent NOx reduction.
- the x-axis indicates the total concentration in ppm (wt.) of the additive component or components for a particular test.
- FIG. 1 illustrates several points:
- HPAO plus EHN combination performed better than the corresponding combination with PIB, in spite of the fact than PIB alone performed better than HPAO alone.
- FIG. 2 depicts the PM emissions that were achieved with the distillate fuels and the additives of FIG. 1 .
- HPAO and EHN alone did not affect PM.
- PIB alone gave slightly increased PM (slightly negative reduction). It may be noted that at about 1600 ppm total concentration, the fuel with 1400 ppm EHN and 200 ppm PIB had improved PM reduction. At about 2400 ppm total concentration, 2100 ppm EHN and 300 ppm PIB, the PM emissions increased (negative reduction).
- 1400 EHN and 200 ppm HPAO gave somewhat increased PM emission, but at about 2400 ppm total concentration, 2100 ppm EHN and 300 PIB gave no PM change.
- FIG. 3 depicts data on one formulation, 10% HPAO/70% EHN in six different distillate fuels that met ASTM D975 specifications, but varied in composition, at various dosages.
- the y-axis is the same as in FIG. 1 , but the x-axis is ppm of the additive as formulated.
- the effectiveness of the additive is clear, but the degree of effectiveness varies from fuel to fuel. For instance, at an additive dosage of 2500 ppm (as formulated) NOx reduction was as high at 7% in the fuel with the best response and as low as about 3% in the fuel with the worst response.
- FIG. 4 is illustrative of this point.
- PM was mitigated by as much as about 7%, whereas in one fuel there was a very slight, and most likely not statistically significant, increase in PM.
- Another different fuel, Fuel E gave a more pronounced negative reduction in PM (increase in PM) than Fuel C. Without being limited to any particular explanation, it may be that this Fuel E behavior was due to high aromatics content and an unusually high specific gravity.
- the present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
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Abstract
Exhaust emissions resulting from the combustion of hydrocarbon fuels in compression ignition engines may be reduced using a homopolymer that may be polyisobutylene, polypropylene, and/or hyperbranched polyalpha-olefins. Optionally, an alkyl nitrate such as 2-ethylhexylnitrate (2EHN), and/or a peroxide, such as hydrogen peroxide, may also be used together with the homopolymer. Both NOx and particulate matter emissions (PM) may be reduced using ppm quantities of the additive compositions; alternatively, NOx emissions may be lowered or reduced while PM emissions do not substantially increase.
Description
- This application claims the benefit of U.S. Provisional Patent Application No. 60/940,914 filed May 30, 2007.
- The present invention relates to additives for distillate fuels, and more particularly relates, in one embodiment to reducing exhaust emissions for hydro-carbon fuels using chemical additives.
- It is well known that considerable effort has been expended reducing the exhaust emissions from compression ignition (e.g. internal combustion) engines. These exhaust emissions are the products of burning the fuel in the engine, emitted from an exhaust system. The major emissions include hydrocarbons, which are unburned or partially burned fuels, nitrogen oxides (generally abbreviated NOx) which are generated when nitrogen in the air reacts with oxygen under the high temperature and pressure conditions inside the engine, carbon monoxide (CO) which is a product of incomplete combustion, and carbon dioxide (CO2) which is a product of the complete combustion of hydrocarbons.
- Additives to fuels are known to reduce undesirable emissions. There are many fuel additives that claim to lower emissions, such as particulate matter, unburnt hydrocarbon, and NOx. Various organo-metallic and totally organic formulations have been proposed and tried. Furthermore, diverse mechanisms have been proposed for their effectiveness.
- It has been found to be difficult to simultaneously reduce particulate matter (PM) emissions and NOx emissions, particularly in diesel fuels. Unfortunately, with some additives, as the PM is lowered, NOx emissions rise, and vice versa with others. There is some promise that ethanol fuel additives may help reduce both PM and NOx simultaneously under certain conditions.
- Thus, it would be desirable if other additives could be developed to reduce the emissions of distillate fuels upon combustion.
- There are provided, in one non-limiting form, compositions for reducing the emissions of distillate fuels that includes a homopolymer such as polyisobutylene (PIB), polypropylene (PP), and/or a hyperbranched polymer. Combinations of these polymeric materials with an alkyl nitrate, such as 2-ethyhexylnitrate (2EHN), and/or a peroxide, such as hydrogen peroxide, are also useful.
- There are further provided in another non-restrictive version distillate fuels, such as diesel fuels, gasoline, jet fuels, or kerosene, having reduced emissions, that contains an effective amount of a composition to reduce emissions of a homopolymer that may be polyisobutylene, polypropylene, and/or a hyperbranched polymer, and optionally an alkyl nitrate and/or a peroxide.
- Also provided in another non-limiting embodiment are methods for reducing emissions of a distillate fuel by adding to the fuel an effective amount of a composition that includes a homopolymer that may be polyisobutylene, polypropylene, and/or a hyperbranched polymer, and optionally an alkyl nitrate and/or a peroxide.
-
FIG. 1 is a graph of NOx emissions in a distillate fuel showing NOx reduction measured as % as a function of total concentration of the additives herein; -
FIG. 2 is a graph of particulate matter emissions measured as a function of the total concentration of the additives for the fuels ofFIG. 1 ; -
FIG. 3 is another graph of NOx emissions in a distillate fuel showing NOx reduction measured as % as a function of total concentration of an additive composition containing 10% hyperbranched polyalpha-olefin (HPAO) and 70% 2-ethylhexyl nitrate (EHN), the balance being solvent; and -
FIG. 4 is a graph of particulate emissions (PM) in a distillate fuel showing NOx reduction measured as % as a function of total concentration of an additive composition containing 10% hyperbranched polyalpha-olefin (HPAO) and 70% 2-ethylhexyl nitrate (EHN), the balance being solvent. - The methods and compositions herein relate to reducing the amount of exhaust emissions resulting from the combustion of hydrocarbon fuels in compression ignition engines such as internal combustion engines. In particular, the additives reduce NOx emissions and/or particulate matter. More specifically, the methods and compositions herein concern a fuel additive formulation that includes a polymer. Suitable polymers are homopolymers including, but not necessarily limited to, polyisobutylene, polypropylene, hyperbranched polymers, and in particular hyperbranched polyalpha-olefins (PAO), and the like. In one non-restrictive version, the hyperbranched polyalpha-olefins may be hyperbranched polymers of C4-C30 alpha-olefins, where the alpha-olefins may be acid- or alcohol-functionalized, and mixtures and derivatives thereof. In one non-limiting embodiment, the polymer presence lowers NOx and in many embodiments also lowers particulate matter (PM).
- The additive composition herein may also optionally contain a component that may be an alkyl nitrate and/or a peroxide. Suitable alkyl nitrates include, but are not necessarily limited to, 2-ethylhexyl nitrate (2EHN), CH3(CH2)3CH(C2H5)CH2ONO2, iso-propyl nitrate, iso-amylnitrate, iso-hexylnitrate, cyclohexyl nitrate, dodecyl nitrate, diglycol nitrate and tetraglycol nitrate and the like. Ether nitrates and fatty acid nitrates may also be useful. The alkyl nitrate may function to primarily lower the NOx emissions although reduction in PM may also be expected. Alternatively, NOx emissions may be lowered by the compositions herein without appreciably raising PM levels, which would also be an advantage and an improvement.
- The additive composition may also optionally include a peroxide, in place of or in addition to the alkyl nitrate. Suitable peroxides include, but are not necessarily limited to, hydrogen peroxide, di-tertiary butyl peroxide, and benzoyl peroxide and the like. Further, some synergism has been found between the homopolymer and the alkyl nitrate and/or peroxide. Known cetane boosters for use in distillate fuels include 2-ethylhexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, and mixtures thereof. Conventional, known ignition accelerators include hydrogen peroxide, benzoyl peroxide, di-tert-butyl peroxide, and the like.
- By hyperbranched polyalpha-olefins are meant polymers prepared by polymerizing hydrocarbons under free radical conditions at low pressures. The polymers are unique in that although hydrocarbon polymers generally have higher molecular weight, greater viscosity and greater hardness than the starting hydro-carbon these polymers generally have higher melting points and congealing points than the starting hydrocarbons. The hydrocarbons employed are primarily alpha-olefins of the formula RCH═CH2 but also include alpha-olefins having vinylidene structures, internal olefins and saturates, where R is an alkyl or alkylene group, including those having vinylidene structures. Suitable hyperbranched polyalpha-olefins are those made according to the methods described in U.S. Pat. Nos. 4,060,569; 4,239,546 and 6,776,808, all incorporated by reference herein in their entirety. The hyperbranched polyalpha-olefins are considered homopolymers herein under the classic definition because they are made from a single monomer. Suitable hyperbranched polyalpha-olefins herein may have a number average molecular weight (Mn) of from about 100 to about 275,000, alternatively a lower threshold of about 150 and independently an upper threshold of about 250,000, and in another non-limiting embodiment from about 200 independently up to about 175,000, or even up to about 125,000 The patents noted above do describe copolymers which are not encompassed by the additive compositions and methods herein.
- Other polymers that may also be useful in the additive compositions herein include, but are not necessarily limited to, isotactic polypropylene (such as ones having a weight average molecular weight in the range of about 2000) or higher molecular weight hyperbranched polymer products than those described above. Polymer alone without the 2EHN may be useful.
- The methods herein relate to additive compositions for distillate fuels, as contrasted with products from resid. In the context herein, distillate fuels include, but are not necessarily limited to diesel fuel, kerosene, gasoline, jet fuel, and the like. It will be appreciated that distillate fuels include blends of conventional hydrocarbons meant by these terms with oxygenates, e.g. alcohols, such as methanol, ethanol, and other additives or blending components presently used in these distillate fuels, such as MTBE (methyl-tert-butyl ether), or that may be used in the future. In one non-limiting embodiment herein, distillate fuels include low sulfur fuels, which are defined as having a sulfur content of 0.2% by weight or less, and in another non-limiting embodiment as having a sulfur content of about 0.0015 wt. % or less—such as the so-called “ultra low sulfur” fuels. Particularly preferred hydrocarbon fuels herein are diesel and kerosene. It is expected that a more conventional diesel fuel (i.e. with an aromatic content of >28%) treated with the additive composition herein will be equivalent in emissions to a Texas Low Emissions Diesel (TxLED) fuel with <10% aromatic content.
- Generally, in one non-limiting embodiment herein the composition for improving the emissions of distillate fuels is a mixture or blend of 2EHN (or a peroxide component) and at least one of the homopolymers. In another non-restrictive version herein the homopolymer is present in the fuel in the range of about 20 to about 2500 ppm, in one non limiting embodiment from about 20 independently up to about 300 ppm; alternatively from about 20 independently up to about 150 ppm. The alkyl nitrate, particularly 2EHN, may be present in the fuel in the range of about 100 to about 3000 ppm, alternatively from about 500, independently up to about 1500 ppm. In one non-limiting embodiment, the volume ratio of homopolymer to the component ranges from about 1:1 to about 1:100, and alternatively the volume ratio of homopolymer to the component ranges from about 1:2 to about 1:10; and in one particularly suitable ratio, about 1:7.
- Typically, a solvent may be advantageously used in the compositions herein, where the solvent may be aromatic solvents and pure paraffinic solvents. Aromatic solvents are particularly preferred. The proportion of solvent in the total fuel additive composition may range from about 0 to 90 weight %; in another non-restrictive embodiment, the solvent may range from a lower threshold of about 15 wt % independently to an upper threshold of 45 wt %. The use of a solvent is optional. In some non-limiting embodiments, no solvent is used or desired. A non-restrictive example would be 87.5% 2EHN and 12.5% HPAO with no solvent (a 7:1 ratio of active components). Specific examples of suitable solvents include, but are not limited to paraffins and cycloparaffins, aromatic naphtha, kerosene, diesel, gasoline, xylene, toluene, alcohols (e.g. 2-ethylhexanol), and the like.
- It will be appreciated that the methods and compositions herein also encompass distillate fuels containing the additive compositions described herein, as well as methods of improving the emissions properties of distillate fuels using the additive compositions described herein.
- Other, optional components of the distillate fuels in non-limiting embodiments may include, but are not necessarily limited to detergents, pour point depressants, cetane improvers, lubricity additives, dehazers, cold operability additives, conductivity additives, biocides, dyes, and mixtures thereof. Particularly useful components may include condensation reaction products of aldehydes and amines which are useful as antioxidants and are effective to lower PM and unburnt hydrocarbon (HC). A specific non-limiting example is the condensation reaction product between formaldehyde and di-n-butylamine. In another non-limiting embodiment, water is explicitly absent from the additive composition.
- The invention will be illustrated further with respect to the following non-limiting Examples that are included only to further illuminate the invention and not to restrict it.
- Additive compositions expected to be useful herein include, but are not necessarily limited to the following outlined in Table I:
-
TABLE I Fuel Additive Compositions to Reduce Exhaust Emissions Ex. Polymer 2EHN Solvent Other 1 10 wt % PIB 70 wt % 15 wt % aromatic 5 wt % 2-ethylhexanol 2 10 wt % 70 wt % 15 wt % aromatic hyperbranched 5 wt % 2-ethylhexanol polymer 3 70 wt % 10 wt % aromatic 20 wt % Product Q
The hyperbranched polymer is a polyalpha-olefin having a molecular weight of about 2800.
The 2-ethylhexanol (2EH) was added as a solvent to improve the low temperature stability of the additive formulation.
Product Q is a condensation reaction product between formaldehyde and di-n-butylamine. - Other additive compositions expected to be useful herein include, but are not necessarily limited to those outlined in Table II:
-
TABLE II Component Description Wt-% Ex. 4 PIB, 1500 MW 10 2-Ethylhexyl nitrate 70 Aromatic solvent 15 2-Ethylhexanol 5 Ex. 5 Hyperbranched PAO 10 2-Ethylhexyl nitrate 70 Aromatic solvent 15 2-Ethylhexanol 5 Ex. 6 2-Ethylhexyl nitrate 70 bis-(dibutyl)diaminomethane 20 Aromatic solvent 10 Ex. 7 PIB, 1500 MW 50 Aromatic solvent 45 2-Ethylhexanol 5 Ex. 8 Hyperbranched PAO 50 Aromatic solvent 45 2-Ethylhexanol 5 Ex. 9 PIB, 1500 MW 10 2-Ethylhexyl nitrate 70 Aromatic solvent 10 Polyester diol (for lubricity) 5 2-Ethylhexanol 5 - The test data in the Figures discussed below was developed using a 1991 DDC Series 60 (Serial No. 06R0038671) heavy duty diesel engine mounted in a transient-capable test cell. This engine had an in-line, six cylinder configuration rated for 365 hp at 1800 rpm, was turbocharged, and used a laboratory water to air heat exchanger for a charge air intercooler. The exhaust was routed to a full flow constant volume sampler that utilized a positive displacement pump. Total flow in the tunnel was maintained at a nominal flow rate of about 2000 SCFM. Sample zone probes for particulate matter (PM), heated oxides of nitrogen (NOx), heated hydrocarbons (HC), carbon monoxide (CO), and carbon dioxide (CO2) measurements were connected to the main tunnel. Probes for background gas measurement were connected downstream of the dilution air filter pack, but upstream of the mixing section. The dilution system was equipped with pressure and temperature sensors at various locations in order to obtain all necessary information required by the U.S. Code of Federal Regulation (40 CFR, Part 86, Subpart N).
-
FIG. 1 depicts the NOx mitigation that is achieved with various formulations of HPAO and PIB, alone and in combination with EHN in a compression ignition fuel. The y-axis indicates the percent NOx reduction. The x-axis indicates the total concentration in ppm (wt.) of the additive component or components for a particular test.FIG. 1 illustrates several points: - 1. All of the formulations mitigated NOx, at least to some extent.
- 2. PIB alone performed considerably better than HPAO alone.
- 3. The combinations of polymer plus EHN performed better than polymer alone or EHN alone.
- 4. The HPAO plus EHN combination performed better than the corresponding combination with PIB, in spite of the fact than PIB alone performed better than HPAO alone.
- 5. The HPAO plus EHN combination performed better at 2000 ppm than EHN alone at 3000. This point becomes even more significant when the fact is considered that the combination product at 2000 ppm has a total of 1600 ppm active components (1400 EHN and 200 HPAO). This clearly indicates a synergism between HPAO and EHN.
-
FIG. 2 depicts the PM emissions that were achieved with the distillate fuels and the additives ofFIG. 1 . HPAO and EHN alone did not affect PM. PIB alone gave slightly increased PM (slightly negative reduction). It may be noted that at about 1600 ppm total concentration, the fuel with 1400 ppm EHN and 200 ppm PIB had improved PM reduction. At about 2400 ppm total concentration, 2100 ppm EHN and 300 ppm PIB, the PM emissions increased (negative reduction). At about 1600 ppm total concentration, 1400 EHN and 200 ppm HPAO gave somewhat increased PM emission, but at about 2400 ppm total concentration, 2100 ppm EHN and 300 PIB gave no PM change. -
FIG. 3 depicts data on one formulation, 10% HPAO/70% EHN in six different distillate fuels that met ASTM D975 specifications, but varied in composition, at various dosages. The y-axis is the same as inFIG. 1 , but the x-axis is ppm of the additive as formulated. In every case the effectiveness of the additive is clear, but the degree of effectiveness varies from fuel to fuel. For instance, at an additive dosage of 2500 ppm (as formulated) NOx reduction was as high at 7% in the fuel with the best response and as low as about 3% in the fuel with the worst response. - In addition to the effectiveness of the HPAO and HPAO-EHN combinations in mitigating NOx, there is clear evidence that these components do so without increasing particulate matter to any significant extent and, in fact, in most cases it actually lowers PM.
FIG. 4 is illustrative of this point. In two of the three fuels PM was mitigated by as much as about 7%, whereas in one fuel there was a very slight, and most likely not statistically significant, increase in PM. Another different fuel, Fuel E, gave a more pronounced negative reduction in PM (increase in PM) than Fuel C. Without being limited to any particular explanation, it may be that this Fuel E behavior was due to high aromatics content and an unusually high specific gravity. - In the foregoing specification, the invention has been described with reference to specific embodiments thereof, and has been demonstrated as effective for reducing the emissions of fuels. However, it will be evident that various modifications and changes can be made thereto without departing from the broader spirit or scope of the invention as set forth in the appended claims. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense. For example, specific combinations of polymers optionally together with alkyl nitrates and/or peroxides falling within the claimed parameters, but not specifically identified or tried in a particular composition to improve the emissions of fuels herein, are expected to be within the scope of this invention. Certain compositions under certain conditions may serve to lower NOx emissions without any substantial increase in PM emissions or with substantially unchanged PM emissions. It is anticipated that the compositions of this invention may also impart to the engines in which they are used as emissions reducers, greater horsepower, and better fuel economy as a result of less friction, whether they are used in diesel or gasoline engines.
- The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
- The words “comprising” and “comprises” as used throughout the claims is to interpreted “including but not limited to”.
Claims (20)
1. A method for reducing emissions of a distillate fuel comprising adding to the distillate fuel an effective amount of an additive composition for reducing the emissions of the distillate fuel, the additive composition comprising a homopolymer selected from the group consisting of polyisobutylene, polypropylene, hyperbranched polymers, and mixtures thereof.
2. The method of claim 1 , where the additive composition further comprises a component selected from the group consisting of an alkyl nitrate, a peroxide and combinations thereof.
3. The method of claim 2 where the effective amount of the component ranges from about 100 to about 3000 ppm and the effective amount of the homopolymer ranges from about 20 to about 2500 ppm, both based on the total distillate fuel.
4. The method of claim 1 where the fuel has reduced NOx and/or particulate matter emissions as compared to an otherwise identical fuel absent the additive composition.
5. The method of claim 1 where the fuel has reduced NOx and particulate matter emissions are substantially the same as or lower compared to an otherwise identical fuel absent the additive composition.
6. A method for reducing emissions of a distillate fuel comprising adding to the distillate fuel an additive composition comprising:
from about 20 to about 2500 ppm, based on the total distillate fuel, of a homopolymer selected from the group consisting of polyisobutylene, polypropylene, hyperbranched polyalpha-olefins, and mixtures thereof; and
from about 100 to about 3000 ppm, based on the total distillate fuel, of a component selected from the group consisting of an alkyl nitrate, a peroxide and combinations thereof.
7. The method of claim 6 where the fuel has reduced NOx and/or particulate matter emissions as compared to an otherwise identical fuel absent the additive composition.
8. The method of claim 6 where the fuel has reduced NOx and particulate matter emissions are substantially the same as or lower compared to an otherwise identical fuel absent the additive composition.
9. An additive composition for reducing the emissions of distillate fuels comprising:
a homopolymer selected from the group consisting of polyisobutylene, polypropylene, hyperbranched polymers, and mixtures thereof; and
a component selected from the group consisting of an alkyl nitrate, a peroxide, and combinations thereof.
10. The composition of claim 9 where the volume ratio of homopolymer to the component ranges from about 1:1 to about 1:100.
11. The composition of claim 9 where the component is an alkyl nitrate selected from the group consisting of 2-ethylhexyl nitrate (2EHN), iso-propyl nitrate, iso-amylnitrate, iso-hexylnitrate, cyclohexyl nitrate, dodecyl nitrate, diglycol nitrate and tetraglycol nitrate.
12. A distillate fuel comprising:
a hydrocarbon selected from the group consisting of diesel fuel, gasoline, jet fuel, and kerosene; and
an effective amount of an additive composition for reducing the emissions of the distillate fuel comprising a homopolymer selected from the group consisting of polyisobutylene, polypropylene, hyperbranched polymers, and mixtures thereof.
13. The distillate of claim 12 where the additive composition further comprises a component selected from the group consisting of an alkyl nitrate, a peroxide, and combinations thereof.
14. The distillate fuel of claim 13 where the effective amount of the component ranges from about 100 to about 3000 ppm and the effective amount of the homopolymer ranges from about 20 to about 2500 ppm, both based on the total distillate fuel.
15. The distillate fuel of claim 12 where the fuel has reduced NOx and/or particulate matter emissions as compared to an otherwise identical fuel absent the additive composition.
16. The distillate fuel of claim 12 where the fuel has reduced NOx and particulate matter emissions are substantially the same or lower as compared to an otherwise identical fuel absent the additive composition.
17. The distillate fuel of claim 13 where the component is an alkyl nitrate selected from the group consisting of 2-ethylhexyl nitrate (2EHN), iso-propyl nitrate, iso-amylnitrate, iso-hexylnitrate, cyclohexyl nitrate, dodecyl nitrate, diglycol nitrate and tetraglycol nitrate.
18. A distillate fuel comprising:
a hydrocarbon selected from the group consisting of diesel fuel, gasoline, jet fuel and kerosene; and
an effective amount of an additive composition for reducing the emissions of the distillate fuel comprising
a homopolymer selected from the group consisting of polyisobutylene, polypropylene, hyperbranched polymers, and mixtures thereof; and
a component selected from the group consisting of an alkyl nitrate, a peroxide, and combinations thereof;
where the fuel has reduced NOx and/or particulate matter emissions as compared to an otherwise identical fuel absent the additive composition.
19. The distillate fuel of claim 18 where the effective amount of the component ranges from about 100 to about 3000 ppm and the effective amount of the homopolymer ranges from about 20 to about 2500 ppm, both based on the total distillate fuel.
20. The distillate fuel of claim 18 where the component is an alkyl nitrate selected from the group consisting of 2-ethylhexyl nitrate (2EHN), iso-propyl nitrate, iso-amylnitrate, iso-hexylnitrate, cyclohexyl nitrate, dodecyl nitrate, diglycol nitrate and tetraglycol nitrate.
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US12/793,463 US20100325944A1 (en) | 2007-05-30 | 2010-06-03 | Additives for Cetane Improvement in Middle Distillate Fuels |
US13/162,761 US20120066964A1 (en) | 2007-05-30 | 2011-06-17 | Additives for Reduction of Exhaust Emissions from Compression Ignition Engines |
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US13/162,761 Continuation-In-Part US20120066964A1 (en) | 2007-05-30 | 2011-06-17 | Additives for Reduction of Exhaust Emissions from Compression Ignition Engines |
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---|---|---|---|---|
WO2011153002A2 (en) * | 2010-06-03 | 2011-12-08 | Baker Hughes In Corporated | Additives for cetane improvement in middle distillate fuels |
US8292976B2 (en) | 2009-11-06 | 2012-10-23 | Afton Chemical Corporation | Diesel fuel additive for reducing emissions |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3227532A (en) * | 1961-08-14 | 1966-01-04 | Exxon Research Engineering Co | Polymer-containing motor fuel composition |
US4060569A (en) * | 1975-12-24 | 1977-11-29 | Petrolite Corporation | Hydrocarbon polymers |
US4239546A (en) * | 1978-07-21 | 1980-12-16 | Petrolite Corporation | Hydrocarbon polymers to improve the hardness of waxes |
US5460633A (en) * | 1991-07-02 | 1995-10-24 | Exxon Chemical Patents Inc. | Fuel oil treatment |
US5906665A (en) * | 1995-09-26 | 1999-05-25 | General Technology Applications, Inc. | High molecular weight fuel additive |
US6048373A (en) * | 1998-11-30 | 2000-04-11 | Ethyl Corporation | Fuels compositions containing polybutenes of narrow molecular weight distribution |
US6200359B1 (en) * | 1998-12-23 | 2001-03-13 | Shell Oil Company | Fuel oil composition |
US6776808B2 (en) * | 2002-08-29 | 2004-08-17 | Baker Hughes Incorporated | Additive to prevent oil separation in paraffin waxes |
US20060201056A1 (en) * | 2000-04-14 | 2006-09-14 | Oryxe Energy International, Inc. | Biodiesel fuel additive |
US20060242894A1 (en) * | 2005-04-27 | 2006-11-02 | Waters Paul F | Low molecular weight fuel additive |
-
2008
- 2008-05-29 US US12/128,918 patent/US20080295395A1/en not_active Abandoned
- 2008-05-30 WO PCT/US2008/065208 patent/WO2008150950A1/en active Search and Examination
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3227532A (en) * | 1961-08-14 | 1966-01-04 | Exxon Research Engineering Co | Polymer-containing motor fuel composition |
US4060569A (en) * | 1975-12-24 | 1977-11-29 | Petrolite Corporation | Hydrocarbon polymers |
US4239546A (en) * | 1978-07-21 | 1980-12-16 | Petrolite Corporation | Hydrocarbon polymers to improve the hardness of waxes |
US5460633A (en) * | 1991-07-02 | 1995-10-24 | Exxon Chemical Patents Inc. | Fuel oil treatment |
US5906665A (en) * | 1995-09-26 | 1999-05-25 | General Technology Applications, Inc. | High molecular weight fuel additive |
US6048373A (en) * | 1998-11-30 | 2000-04-11 | Ethyl Corporation | Fuels compositions containing polybutenes of narrow molecular weight distribution |
US6200359B1 (en) * | 1998-12-23 | 2001-03-13 | Shell Oil Company | Fuel oil composition |
US20060201056A1 (en) * | 2000-04-14 | 2006-09-14 | Oryxe Energy International, Inc. | Biodiesel fuel additive |
US6776808B2 (en) * | 2002-08-29 | 2004-08-17 | Baker Hughes Incorporated | Additive to prevent oil separation in paraffin waxes |
US20060242894A1 (en) * | 2005-04-27 | 2006-11-02 | Waters Paul F | Low molecular weight fuel additive |
US20060254131A1 (en) * | 2005-04-27 | 2006-11-16 | Waters Paul F | Low molecular weight fuel additive |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8292976B2 (en) | 2009-11-06 | 2012-10-23 | Afton Chemical Corporation | Diesel fuel additive for reducing emissions |
WO2011153002A2 (en) * | 2010-06-03 | 2011-12-08 | Baker Hughes In Corporated | Additives for cetane improvement in middle distillate fuels |
WO2011153002A3 (en) * | 2010-06-03 | 2012-03-08 | Baker Hughes In Corporated | Additives for cetane improvement in middle distillate fuels |
Also Published As
Publication number | Publication date |
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WO2008150950A1 (en) | 2008-12-11 |
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