CA2315683A1 - Ignition improved fuels - Google Patents
Ignition improved fuels Download PDFInfo
- Publication number
- CA2315683A1 CA2315683A1 CA002315683A CA2315683A CA2315683A1 CA 2315683 A1 CA2315683 A1 CA 2315683A1 CA 002315683 A CA002315683 A CA 002315683A CA 2315683 A CA2315683 A CA 2315683A CA 2315683 A1 CA2315683 A1 CA 2315683A1
- Authority
- CA
- Canada
- Prior art keywords
- ketone
- fuel
- cyclic
- peroxides
- peroxide
- 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
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 99
- -1 cyclic ketone peroxide Chemical class 0.000 claims abstract description 99
- 150000002978 peroxides Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 231100000719 pollutant Toxicity 0.000 claims abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 36
- 150000002576 ketones Chemical class 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002283 diesel fuel Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 13
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 12
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 claims description 12
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 12
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 claims description 12
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 12
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 5
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N methyl iso-propyl ketone Natural products CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- AUAWVMRINGOBFE-UHFFFAOYSA-N nitroso hydrogen carbonate Chemical compound OC(=O)ON=O AUAWVMRINGOBFE-UHFFFAOYSA-N 0.000 claims description 2
- 125000006755 (C2-C20) alkyl group Chemical group 0.000 claims 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- 208000007976 Ketosis Diseases 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 150000002584 ketoses Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019401 acetone peroxide Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940032007 methylethyl ketone Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- NKXMBTKMOVMBPH-UHFFFAOYSA-N 1-phenylpentane-1,3-dione Chemical compound CCC(=O)CC(=O)C1=CC=CC=C1 NKXMBTKMOVMBPH-UHFFFAOYSA-N 0.000 description 1
- NROOHYGFTHTDFF-UHFFFAOYSA-N 1-phenylpentane-2,4-dione Chemical compound CC(=O)CC(=O)CC1=CC=CC=C1 NROOHYGFTHTDFF-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- IEBAJFDSHJYDCK-UHFFFAOYSA-N 2-methylundecan-4-one Chemical compound CCCCCCCC(=O)CC(C)C IEBAJFDSHJYDCK-UHFFFAOYSA-N 0.000 description 1
- LCLCVVVHIPPHCG-UHFFFAOYSA-N 5,5-dimethylhexane-2,4-dione Chemical compound CC(=O)CC(=O)C(C)(C)C LCLCVVVHIPPHCG-UHFFFAOYSA-N 0.000 description 1
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 description 1
- IGMOYJSFRIASIE-UHFFFAOYSA-N 6-Methylheptan-2,4-dione Chemical compound CC(C)CC(=O)CC(C)=O IGMOYJSFRIASIE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000011 acetone peroxide Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008264 cloud Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- QSOMFNQEXNFPNU-UHFFFAOYSA-L magnesium;hydrogen sulfate;hydroxide;hydrate Chemical compound O.O.[Mg+2].[O-]S([O-])(=O)=O QSOMFNQEXNFPNU-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- PJEPOHXMGDEIMR-UHFFFAOYSA-N octane-3,5-dione Chemical compound CCCC(=O)CC(=O)CC PJEPOHXMGDEIMR-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
- C10L1/2286—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen triple bonds, e.g. nitriles
-
- 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
- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
-
- 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
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Abstract
A fuel is presented which is doped with 0.01-10 % by weight of cyclic ketone peroxide(s), characterized in that it comprises from 0.01 to 10 percent by weight of cyclic ketone peroxides of formula (I) wherein R1-R6 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, which groups may include linear or branched alkyl moieties; and each of R1-R6 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrile, and amido, with the proviso that said peroxides make up at least 35 % by weight of all peroxides in the fuel, to reduce the emission of pollutants when the fuel is used in a combustion engine. Also the process to make such fuels is presented.
Description
IGNITION IMPROVED FUELS
The invention relates to fuels with improved ignition characteristics comprising one or more ketone peroxides, as well as to a process to prepare such fuels.
The use of peroxides in fuels has long been common knowledge. Back in the 1940s US 2,378,341 disclosed the use of a peroxide of a hydrocarbon having at least one aliphatic tertiary carbon atom, the peroxy radical in said peroxide connecting two tertiary carbon atoms, while Ind. Eng. Chem., Vol. 41, No. 8, pp.
1679-1682 disclosed the use of di-tert-butyl peroxide and 2,2-bis(tert-butylperoxy)butane for the purpose of improving the ignition of diesel fuels.
Also, FR-B-862,070 disclosed a very hazardous process which is conducted at undesired low temperatures to make polymeric ketone peroxides from mixtures of aliphatic ketones, and their use in fuel. The products are said to have improved solubility in the fuel and a low crystallization temperature.
FR-B-862,974 discloses the production of certain cyclic ketone peroxides and their use in diesel fuel to improve the ignition characteristics.
In 1961, US 3,003,000 disclosed ketone peroxides and oligomeric ketone peroxides, a process to make them, and their generic use in, inter alia, diesel fuels. The process also yields some cyclic ketone peroxide by-products. These by-products are present in the oligomeric ketone peroxides in trace amounts.
Also, the use in diesel fuel formulations is not exemplified.
US 3,116,300 (published in 1963) discloses dimeric cyclic ketone peroxides, viz. the product formed when two ketone molecules are reacted.
Ignition improvers are desired for use in hydrocarbon distillates and residue-containing oils that are useful as fuels for combustion engines except for their ignition characteristics. Usually, such fuels suffer from a too long ignition lag, i.e., the time between the injection of the fuel into the zone of combustion, as in directly injected engines such as diesel engines, and the moment the fuel ignites, or the time between the activation of external ignition sources, such as spark plugs, and the moment the fuel ignites. As a result, poor combustion efficiency and rough engine operation are observed, with all attendant adverse consequences. The term improved ignition, therefore, means that in combustion engines fuel is burned with improved efficiency, which usually is obvious from the higher cetane number of the fuel and the reduced emission of pollutants upon combustion of the fuel in said engine. As is well-known, the use of diesel fuel with improved ignition can result in reductions of the hydrocarbon, carbon monoxide, NOx, and particulate matter (soot) emissions. Depending on the type of fuel and the type and quantity of ignition improver used, reductions of 40% of said emissions are quite feasible.
Despite the time lapse since the invention of ketone peroxides, they have not found any commercial use as an ignition improver. On the contrary, the presently used commercial products to improve the ignition of (diesel) fuels are di-tert-butyl peroxide and 2-ethylhexyl nitrate, as taught by Chemtech, 8-97, pp.
38-41. However, these products suffer from various disadvantages. Nitrates may lead to NOx formation upon combustion, while di-tert-butyl peroxide has a low flash-point and high volatility, which can lead to various safety hazards.
Nor do most peroxides possess long-term (thermal) stability in diesel fuels.
Especially at higher temperatures such as can be encountered in fuel systems, decreased thermal stability can lead to gum formation or other degradation of the fuel. Also, the decomposition products of peroxides generally are (partly) alcoholic in nature, which tends to increase the undesired water uptake by the fuel. Furthermore, most of the peroxides used thus far suffer from a relatively low active matter content. Also, the price/performance ratio of most peroxides stands in the way of their being widely introduced into (diesel) fuels. In this respect it is noted that the unsatisfactory performance of dimeric cyclic ketone peroxides as disclosed in, for instance, FR-B-862,974 is considered to lead to an unacceptable price/performance ratio of these products. Furthermore, the dimeric structure of conventional cyclic ketone peroxides may present a safety hazard, due to the volatility and the low flash point of such products. In consequence, there still is a need for fuels with improved characteristics.
Surprisingly, some of the peroxide compositions disclosed in WO 96/03397 were found to be very suitable for improving the ignition characteristics of fuels.
WO 96/03397 relates to numerous formulations of cyclic ketone peroxides, as described below, comprising a variety of phlegmatizers. However, this patent application does not disclose or suggest the use of cyclic ketone peroxides in fuels. A comparison between the cyclic ketone peroxides of WO 96/03397 that perform well and the cyclic ketone peroxides according to, for example, FR-B-862,974 showed that the surprising performance is related to the nature of the cyclic ketone peroxide that is used. Therefore, the invention resides in the proper selection of the ketone peroxide used to improve the fuel.
The fuel according to the invention is characterized in that it comprises from 0.001 to 10 percent by weight of one or more cyclic ketone peroxides selected from the group of peroxides represented by formula I:
wherein R,, R3, and R5 are independently selected from the group consisting of hydrogen, C,-Coo alkyl, C3-CZO cycloalkyl, Cs C2o aryl, C,-C2o aralkyl, and C,-CZo alkaryl, which groups may include linear or branched alkyl moieties, and R2, R4, and Re are independently selected from the group consisting of hydrogen, C2 Coo alkyl, C3-Coo cycloalkyl, Cg-Coo aryl, C; Coo aralkyl, and C,-Coo alkaryl, which groups may include linear or branched alkyl moieties; and each of R,-R6 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrite, and amido, with the proviso that said peroxides make up at least 35% by weight of all cyclic ketone peroxides in the fuel.
The improved fuels according to the invention do not suffer from most of the disadvantages mentioned above. More specifically, it was found that the use of the cyclic ketone peroxides of formula I results in fuels with an exceptionally good performance with respect to ignition timing and the correlated cetane number, good miscibility, good chemical stability, i.e. resistance to oxygen, acids, and metal oxides such as rust, and good compatibility with other parts of the fuel system, such as metals, rubber fittings, gaskets, and hoses.
Preferably, the cyclic ketone peroxides according to the invention consist of oxygen, carbon, and hydrogen atoms, so as to avoid an adverse effect on the NOx emission upon combustion of the fuel into which they are incorporated.
More preferably, the cyclic ketone peroxides according to formula I are derived from at least one ketone with a molecular weight greater than acetone, such that the total number of carbon atoms of the molecule is greater than 6. The use of such ketones of higher molecular weight will have a positive effect on the solubility of said cyclic ketone peroxide in a fuel and was found to more effective as an ignition improver, based on the amount of active oxygen added.
Preferably, a ketone with at least 4 carbon atoms, more preferably with at least 5 carbon atoms, is used to produce the cyclic ketone peroxide used according to the invention. Also, the total number of carbon atoms in the cyclic ketone peroxide according to the invention preferably is less than 40, more preferably less than 30, and most preferably less than 25. Otherwise the molecular weight will be too high, necessitating a high dosing level of the peroxide to the fuel, which is economically unattractive. Incidentally, it is noted that if mixtures of ketones comprising acetone are used, then some undesired dimeric and trimeric acetone peroxides will be formed. Such cyclic acetone peroxides can precipitate at lower temperatures when used in a fuel, particularly in a diesel fuel, and thus may necessitate a further purification step. Hence also the use of acetone in mixtures of ketones is undesired. Furthermore, although mixtures of 5 ketones can be used to make the cyclic ketone peroxides according to the invention, it is preferred that just one ketone is used, such that R,=R3=R5 and R2=R4=Re. Such cyclic ketone peroxides are, inter alia, more easily produced and less prone to changes in composition due to changing process conditions.
Hence, the quality of the ignition improvers thus formed is mote easily controlled.
The ignition time improving cyclic ketone peroxides) preferably is/are present in such an amount that the self ignition time of treated fuel is shorter in a model test as described below than the self-ignition time of untreated fuel. More preferably, a reduction of the self ignition time by more than 10% is observed at 270°C in said test. Even more preferably, the reduction of the self ignition time is more than 25% at this test temperature. Most preferred is a reduction of at least 50% of the self ignition time at 270°C.
Preferably, one or more of the cyclic ketone peroxides according to formula I
are present in the final fuel formulation in an amount of between 0.025 and 5 percent by weight (% w/w). Most preferred is a concentration of cyclic peroxide of formula I in the fuel of between 0.05 and 2.5% w/w. Less peroxide will not result in any noticeable improvement of the ignition characteristics of the fuel, whereas a higher amount may prove to be unsafe or uneconomical.
The term fuels, as used throughout this document, is meant to encompass all hydrocarbon distillates and residue-containing oils for use in combustion engines and which distil) between the kerosene fraction and the lubricating oil fraction of petroleum. The fuel may comprise the usual additives, such as anti-foam agents, injector cleaning agents, drying agents, cloud point depressants, also known as anti-gel agents, algea control agents, lubricants, dyes, and oxidation inhibitors, but may also comprise further ignition improving or combustion improving additives, provided that such additives do not adversely affect the storage stability of the final fuel composition according to the invention. A preferred fuel is diesel fuel.
In a second embodiment, the invention relates to a process to make the ignition improved fuels. To this end, an appropriate cyclic ketone peroxide composition is combined with a fuel, or else the cyclic ketone peroxide is produced directly in said fuel.
The cyclic ketone peroxides) can be produced as described in WO 96/03397.
It is disclosed there how by changing the reaction conditions, the composition of the resulting cyclic ketone peroxide can be controlled. The trimeric cyclic ketone peroxides according to formula I preferably are formed when mild reaction conditions are chosen, e.g. by lowering the amount of acid used in the process, lowering the temperature, reacting for a short period of time, and/or dosing the hydrogen peroxide and the acid at the same time. Furthermore, the production of the trimeric compound is favoured when less water is used in the reaction, probably because less trimeric compound is hydrolyzed to the dimeric compound. The exact conditions will depend on the type of ketone that is used and the concentration of the various reactants. However, the skilled person will have no problem in determining which process conditions are to be selected for producing the cyclic ketone peroxides as used in the invention. Preferably, however, the process temperature ranges from 0-80°C, more preferably 5-60°C, and most preferably 20-45°C to allow for a cost-efficient process.
Suitable ketones for use in the synthesis of cyclic ketone peroxides as used in the invention include, for example, acetone, acetophenone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, dimethyl ketone, diethylketone, dipropyl ketone, methylethyl ketone, methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-tert-butyl ketone, isobutylheptyl ketone, diisobutyl ketone, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 3,5-octanedione, 5-methyl-2,4-hexanedione, 2,6-dimethyl-3,5-heptanedione, 2,4-octanedione, 5,5-dimethyl-2,4-hexanedione, 6-methyl-2,4-heptanedione, 1-phenyl-1,3-butanedione, 1-phenyl-1,3-pentanedione, 1,3-Biphenyl-1,3-propanedione, 1-phenyl-2,4-pentanedione, methylbenzyl ketone, phenylmethyl ketone, phenylethyl ketone, and coupling products thereof. Of course, other ketones having appropriate R
groups corresponding to the peroxides of formula I can also be employed, as well as mixtures of two or more different ketones.
Examples of preferred peroxides of formula I for use in accordance with the present invention are the cyclic ketone peroxides derived from methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, isomers of these ketones, and mixtures thereof. More preferably, the peroxides of formula I are based on at least one ketone selected from the group consisting of methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, and one or more isomers of these ketones, such as methyl-isobutyl ketone and methyiisopropyl ketone.
The peroxides can be prepared, transported, stored, and applied in any solid or liquid form, but solutions in a non-halogenated liquid phlegmatiser are preferred. These compositions can then be combined with the fuel. It should be noted that certain phlegmatizers may not be suitable for use in all of the ketone peroxide compositions of the present invention. More particularly, in order to obtain a safe composition, the phlegmatizer should have a certain minimum flash point and minimum boiling point relative to the decomposition temperature of the ketone peroxide, such that the phlegmatizer cannot be boiled off leaving a concentrated, unsafe ketone peroxide composition.
Preferred phlegmatizers are selected from the group consisting of hydrocarbons, such as (diesel) fuel, paraffinic and white oils, oxygenated hydrocarbons, such as, ethers, aldehydes, epoxides, esters, ketones, alcohols, and organic peroxides, such as linear ketone peroxides and di-tert-butyl peroxide, alkyl nitrates, such as 2-ethylhexyl nitrate, and mixtures thereof.
Examples of preferred liquid phlegmatizers for the cyclic ketone peroxides include alkanols, in particular higher aliphatic alkanols, cycloalkanols, alkylene glycols, alkylene glycol monoalkyl ethers, ethers, in particular methyl tert-butyl ether, aldehydes, ketones, epoxides, esters, hydrocarbon solvents, including toluene, xylene, (diesel) fuel, paraffinic oils, and white oils. More preferred iiquid phlegmatizers are ethers and hydrocarbons. Most preferably, a fuel is used as the phlegmatiser. A concentrated cyclic ketone peroxide composition is very suitable for further dilution with fuel in order to obtain a fuel comprising an ignition improving amount of said peroxide.
The fuel according to the invention may contain just peroxides of formula I as the ignition improver. However, they may also be combined with other ignition improvers, such as . conventional di-tert-butyl peroxide and/or 2-ethyihexyl nitrate. If the peroxides of formula I are used together with other cyclic ketone peroxide ignition improvers, then it is preferred that they make up at least 40%
w/w, more preferably at least 45% w/w, more preferably at least 50% w/w, more preferably at least 66% w/w, and even more preferably more than 75% w/w, based on the weight of ali cyclic ketone peroxides in the fuel. Most preferred are compositions in which more than 80% wlw of the weight of all cyclic ketone peroxides can be attributed to cyclic ketone peroxides according to formula I, because the ignition properties of such fuels is most efficiently improved. If only cyclic ketone peroxides consisting essentially of a mixture of dimeric and trimeric compounds (according to formula I) are used in the fuel, then the indicated preferred ranges show that the ratio of dimeric to trimeric compounds in the fuel is lower than about 2:1, more preferably lower than about 3:2, more preferably lower than about 5:4, more preferably tower than about 1:1, more preferably lower than 1:2, more preferably lower than about 1:3, and most preferably lower than about 1:4.
To avoid safety hazards, it is preferred that the cyclic ketone peroxide composition used to make up the claimed fuels is not essentially pure cyclic ketone peroxide. More preferably, the compositions comprise less than 99%
w/w, more preferably less than 90% w/w, and even more preferably less than 85% w/w of cyclic ketone peroxide, all based on the weight of the total formulation. Most preferably, the cyclic ketone peroxide composition that is used to make fuels according to the invention comprises less than 75% w/w of cyclic ketone peroxide, based on the weight of the total composition.
Alternatively, the cyclic ketone peroxides can be prepared in a fuel, which can be the fuel the ignition characteristics of which are to be improved, in the desired concentration of between 0.01 and 10% w/w. To this end, the conventional reactants and catalysts) are introduced into untreated fuel and reacted. Subsequently, the ignition improved fuel is separated from contaminants and process water, optionally washed, and optionally dried, all in a conventional manner. In this preparation, the streams to be processed are quite large in volume, but the handling of a peroxide concentrate can be avoided.
The invention is elucidated by the following examples.
Examples Materials used:
Isopar~ M hydrocarbon phlegmatizer ex Exxon Chemical 5 Cyclic-MEKP-1 cyclic methyl-ethyl-ketone peroxide (41 % w/w in Isopar M) ex Akzo Nobel 93% trimeric, 7% dimeric compounds (GC
area%) Cyclic-MEKP-2 cyclic methyl-ethyl-ketone peroxide (29.7% w/w in Diesel 1 ) ex Akzo Nobel 85% trimeric, 15% dimeric compounds (GC
The invention relates to fuels with improved ignition characteristics comprising one or more ketone peroxides, as well as to a process to prepare such fuels.
The use of peroxides in fuels has long been common knowledge. Back in the 1940s US 2,378,341 disclosed the use of a peroxide of a hydrocarbon having at least one aliphatic tertiary carbon atom, the peroxy radical in said peroxide connecting two tertiary carbon atoms, while Ind. Eng. Chem., Vol. 41, No. 8, pp.
1679-1682 disclosed the use of di-tert-butyl peroxide and 2,2-bis(tert-butylperoxy)butane for the purpose of improving the ignition of diesel fuels.
Also, FR-B-862,070 disclosed a very hazardous process which is conducted at undesired low temperatures to make polymeric ketone peroxides from mixtures of aliphatic ketones, and their use in fuel. The products are said to have improved solubility in the fuel and a low crystallization temperature.
FR-B-862,974 discloses the production of certain cyclic ketone peroxides and their use in diesel fuel to improve the ignition characteristics.
In 1961, US 3,003,000 disclosed ketone peroxides and oligomeric ketone peroxides, a process to make them, and their generic use in, inter alia, diesel fuels. The process also yields some cyclic ketone peroxide by-products. These by-products are present in the oligomeric ketone peroxides in trace amounts.
Also, the use in diesel fuel formulations is not exemplified.
US 3,116,300 (published in 1963) discloses dimeric cyclic ketone peroxides, viz. the product formed when two ketone molecules are reacted.
Ignition improvers are desired for use in hydrocarbon distillates and residue-containing oils that are useful as fuels for combustion engines except for their ignition characteristics. Usually, such fuels suffer from a too long ignition lag, i.e., the time between the injection of the fuel into the zone of combustion, as in directly injected engines such as diesel engines, and the moment the fuel ignites, or the time between the activation of external ignition sources, such as spark plugs, and the moment the fuel ignites. As a result, poor combustion efficiency and rough engine operation are observed, with all attendant adverse consequences. The term improved ignition, therefore, means that in combustion engines fuel is burned with improved efficiency, which usually is obvious from the higher cetane number of the fuel and the reduced emission of pollutants upon combustion of the fuel in said engine. As is well-known, the use of diesel fuel with improved ignition can result in reductions of the hydrocarbon, carbon monoxide, NOx, and particulate matter (soot) emissions. Depending on the type of fuel and the type and quantity of ignition improver used, reductions of 40% of said emissions are quite feasible.
Despite the time lapse since the invention of ketone peroxides, they have not found any commercial use as an ignition improver. On the contrary, the presently used commercial products to improve the ignition of (diesel) fuels are di-tert-butyl peroxide and 2-ethylhexyl nitrate, as taught by Chemtech, 8-97, pp.
38-41. However, these products suffer from various disadvantages. Nitrates may lead to NOx formation upon combustion, while di-tert-butyl peroxide has a low flash-point and high volatility, which can lead to various safety hazards.
Nor do most peroxides possess long-term (thermal) stability in diesel fuels.
Especially at higher temperatures such as can be encountered in fuel systems, decreased thermal stability can lead to gum formation or other degradation of the fuel. Also, the decomposition products of peroxides generally are (partly) alcoholic in nature, which tends to increase the undesired water uptake by the fuel. Furthermore, most of the peroxides used thus far suffer from a relatively low active matter content. Also, the price/performance ratio of most peroxides stands in the way of their being widely introduced into (diesel) fuels. In this respect it is noted that the unsatisfactory performance of dimeric cyclic ketone peroxides as disclosed in, for instance, FR-B-862,974 is considered to lead to an unacceptable price/performance ratio of these products. Furthermore, the dimeric structure of conventional cyclic ketone peroxides may present a safety hazard, due to the volatility and the low flash point of such products. In consequence, there still is a need for fuels with improved characteristics.
Surprisingly, some of the peroxide compositions disclosed in WO 96/03397 were found to be very suitable for improving the ignition characteristics of fuels.
WO 96/03397 relates to numerous formulations of cyclic ketone peroxides, as described below, comprising a variety of phlegmatizers. However, this patent application does not disclose or suggest the use of cyclic ketone peroxides in fuels. A comparison between the cyclic ketone peroxides of WO 96/03397 that perform well and the cyclic ketone peroxides according to, for example, FR-B-862,974 showed that the surprising performance is related to the nature of the cyclic ketone peroxide that is used. Therefore, the invention resides in the proper selection of the ketone peroxide used to improve the fuel.
The fuel according to the invention is characterized in that it comprises from 0.001 to 10 percent by weight of one or more cyclic ketone peroxides selected from the group of peroxides represented by formula I:
wherein R,, R3, and R5 are independently selected from the group consisting of hydrogen, C,-Coo alkyl, C3-CZO cycloalkyl, Cs C2o aryl, C,-C2o aralkyl, and C,-CZo alkaryl, which groups may include linear or branched alkyl moieties, and R2, R4, and Re are independently selected from the group consisting of hydrogen, C2 Coo alkyl, C3-Coo cycloalkyl, Cg-Coo aryl, C; Coo aralkyl, and C,-Coo alkaryl, which groups may include linear or branched alkyl moieties; and each of R,-R6 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrite, and amido, with the proviso that said peroxides make up at least 35% by weight of all cyclic ketone peroxides in the fuel.
The improved fuels according to the invention do not suffer from most of the disadvantages mentioned above. More specifically, it was found that the use of the cyclic ketone peroxides of formula I results in fuels with an exceptionally good performance with respect to ignition timing and the correlated cetane number, good miscibility, good chemical stability, i.e. resistance to oxygen, acids, and metal oxides such as rust, and good compatibility with other parts of the fuel system, such as metals, rubber fittings, gaskets, and hoses.
Preferably, the cyclic ketone peroxides according to the invention consist of oxygen, carbon, and hydrogen atoms, so as to avoid an adverse effect on the NOx emission upon combustion of the fuel into which they are incorporated.
More preferably, the cyclic ketone peroxides according to formula I are derived from at least one ketone with a molecular weight greater than acetone, such that the total number of carbon atoms of the molecule is greater than 6. The use of such ketones of higher molecular weight will have a positive effect on the solubility of said cyclic ketone peroxide in a fuel and was found to more effective as an ignition improver, based on the amount of active oxygen added.
Preferably, a ketone with at least 4 carbon atoms, more preferably with at least 5 carbon atoms, is used to produce the cyclic ketone peroxide used according to the invention. Also, the total number of carbon atoms in the cyclic ketone peroxide according to the invention preferably is less than 40, more preferably less than 30, and most preferably less than 25. Otherwise the molecular weight will be too high, necessitating a high dosing level of the peroxide to the fuel, which is economically unattractive. Incidentally, it is noted that if mixtures of ketones comprising acetone are used, then some undesired dimeric and trimeric acetone peroxides will be formed. Such cyclic acetone peroxides can precipitate at lower temperatures when used in a fuel, particularly in a diesel fuel, and thus may necessitate a further purification step. Hence also the use of acetone in mixtures of ketones is undesired. Furthermore, although mixtures of 5 ketones can be used to make the cyclic ketone peroxides according to the invention, it is preferred that just one ketone is used, such that R,=R3=R5 and R2=R4=Re. Such cyclic ketone peroxides are, inter alia, more easily produced and less prone to changes in composition due to changing process conditions.
Hence, the quality of the ignition improvers thus formed is mote easily controlled.
The ignition time improving cyclic ketone peroxides) preferably is/are present in such an amount that the self ignition time of treated fuel is shorter in a model test as described below than the self-ignition time of untreated fuel. More preferably, a reduction of the self ignition time by more than 10% is observed at 270°C in said test. Even more preferably, the reduction of the self ignition time is more than 25% at this test temperature. Most preferred is a reduction of at least 50% of the self ignition time at 270°C.
Preferably, one or more of the cyclic ketone peroxides according to formula I
are present in the final fuel formulation in an amount of between 0.025 and 5 percent by weight (% w/w). Most preferred is a concentration of cyclic peroxide of formula I in the fuel of between 0.05 and 2.5% w/w. Less peroxide will not result in any noticeable improvement of the ignition characteristics of the fuel, whereas a higher amount may prove to be unsafe or uneconomical.
The term fuels, as used throughout this document, is meant to encompass all hydrocarbon distillates and residue-containing oils for use in combustion engines and which distil) between the kerosene fraction and the lubricating oil fraction of petroleum. The fuel may comprise the usual additives, such as anti-foam agents, injector cleaning agents, drying agents, cloud point depressants, also known as anti-gel agents, algea control agents, lubricants, dyes, and oxidation inhibitors, but may also comprise further ignition improving or combustion improving additives, provided that such additives do not adversely affect the storage stability of the final fuel composition according to the invention. A preferred fuel is diesel fuel.
In a second embodiment, the invention relates to a process to make the ignition improved fuels. To this end, an appropriate cyclic ketone peroxide composition is combined with a fuel, or else the cyclic ketone peroxide is produced directly in said fuel.
The cyclic ketone peroxides) can be produced as described in WO 96/03397.
It is disclosed there how by changing the reaction conditions, the composition of the resulting cyclic ketone peroxide can be controlled. The trimeric cyclic ketone peroxides according to formula I preferably are formed when mild reaction conditions are chosen, e.g. by lowering the amount of acid used in the process, lowering the temperature, reacting for a short period of time, and/or dosing the hydrogen peroxide and the acid at the same time. Furthermore, the production of the trimeric compound is favoured when less water is used in the reaction, probably because less trimeric compound is hydrolyzed to the dimeric compound. The exact conditions will depend on the type of ketone that is used and the concentration of the various reactants. However, the skilled person will have no problem in determining which process conditions are to be selected for producing the cyclic ketone peroxides as used in the invention. Preferably, however, the process temperature ranges from 0-80°C, more preferably 5-60°C, and most preferably 20-45°C to allow for a cost-efficient process.
Suitable ketones for use in the synthesis of cyclic ketone peroxides as used in the invention include, for example, acetone, acetophenone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylisoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, dimethyl ketone, diethylketone, dipropyl ketone, methylethyl ketone, methylisobutyl ketone, methylisopropyl ketone, methylpropyl ketone, methyl-tert-butyl ketone, isobutylheptyl ketone, diisobutyl ketone, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 3,5-octanedione, 5-methyl-2,4-hexanedione, 2,6-dimethyl-3,5-heptanedione, 2,4-octanedione, 5,5-dimethyl-2,4-hexanedione, 6-methyl-2,4-heptanedione, 1-phenyl-1,3-butanedione, 1-phenyl-1,3-pentanedione, 1,3-Biphenyl-1,3-propanedione, 1-phenyl-2,4-pentanedione, methylbenzyl ketone, phenylmethyl ketone, phenylethyl ketone, and coupling products thereof. Of course, other ketones having appropriate R
groups corresponding to the peroxides of formula I can also be employed, as well as mixtures of two or more different ketones.
Examples of preferred peroxides of formula I for use in accordance with the present invention are the cyclic ketone peroxides derived from methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, isomers of these ketones, and mixtures thereof. More preferably, the peroxides of formula I are based on at least one ketone selected from the group consisting of methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, and one or more isomers of these ketones, such as methyl-isobutyl ketone and methyiisopropyl ketone.
The peroxides can be prepared, transported, stored, and applied in any solid or liquid form, but solutions in a non-halogenated liquid phlegmatiser are preferred. These compositions can then be combined with the fuel. It should be noted that certain phlegmatizers may not be suitable for use in all of the ketone peroxide compositions of the present invention. More particularly, in order to obtain a safe composition, the phlegmatizer should have a certain minimum flash point and minimum boiling point relative to the decomposition temperature of the ketone peroxide, such that the phlegmatizer cannot be boiled off leaving a concentrated, unsafe ketone peroxide composition.
Preferred phlegmatizers are selected from the group consisting of hydrocarbons, such as (diesel) fuel, paraffinic and white oils, oxygenated hydrocarbons, such as, ethers, aldehydes, epoxides, esters, ketones, alcohols, and organic peroxides, such as linear ketone peroxides and di-tert-butyl peroxide, alkyl nitrates, such as 2-ethylhexyl nitrate, and mixtures thereof.
Examples of preferred liquid phlegmatizers for the cyclic ketone peroxides include alkanols, in particular higher aliphatic alkanols, cycloalkanols, alkylene glycols, alkylene glycol monoalkyl ethers, ethers, in particular methyl tert-butyl ether, aldehydes, ketones, epoxides, esters, hydrocarbon solvents, including toluene, xylene, (diesel) fuel, paraffinic oils, and white oils. More preferred iiquid phlegmatizers are ethers and hydrocarbons. Most preferably, a fuel is used as the phlegmatiser. A concentrated cyclic ketone peroxide composition is very suitable for further dilution with fuel in order to obtain a fuel comprising an ignition improving amount of said peroxide.
The fuel according to the invention may contain just peroxides of formula I as the ignition improver. However, they may also be combined with other ignition improvers, such as . conventional di-tert-butyl peroxide and/or 2-ethyihexyl nitrate. If the peroxides of formula I are used together with other cyclic ketone peroxide ignition improvers, then it is preferred that they make up at least 40%
w/w, more preferably at least 45% w/w, more preferably at least 50% w/w, more preferably at least 66% w/w, and even more preferably more than 75% w/w, based on the weight of ali cyclic ketone peroxides in the fuel. Most preferred are compositions in which more than 80% wlw of the weight of all cyclic ketone peroxides can be attributed to cyclic ketone peroxides according to formula I, because the ignition properties of such fuels is most efficiently improved. If only cyclic ketone peroxides consisting essentially of a mixture of dimeric and trimeric compounds (according to formula I) are used in the fuel, then the indicated preferred ranges show that the ratio of dimeric to trimeric compounds in the fuel is lower than about 2:1, more preferably lower than about 3:2, more preferably lower than about 5:4, more preferably tower than about 1:1, more preferably lower than 1:2, more preferably lower than about 1:3, and most preferably lower than about 1:4.
To avoid safety hazards, it is preferred that the cyclic ketone peroxide composition used to make up the claimed fuels is not essentially pure cyclic ketone peroxide. More preferably, the compositions comprise less than 99%
w/w, more preferably less than 90% w/w, and even more preferably less than 85% w/w of cyclic ketone peroxide, all based on the weight of the total formulation. Most preferably, the cyclic ketone peroxide composition that is used to make fuels according to the invention comprises less than 75% w/w of cyclic ketone peroxide, based on the weight of the total composition.
Alternatively, the cyclic ketone peroxides can be prepared in a fuel, which can be the fuel the ignition characteristics of which are to be improved, in the desired concentration of between 0.01 and 10% w/w. To this end, the conventional reactants and catalysts) are introduced into untreated fuel and reacted. Subsequently, the ignition improved fuel is separated from contaminants and process water, optionally washed, and optionally dried, all in a conventional manner. In this preparation, the streams to be processed are quite large in volume, but the handling of a peroxide concentrate can be avoided.
The invention is elucidated by the following examples.
Examples Materials used:
Isopar~ M hydrocarbon phlegmatizer ex Exxon Chemical 5 Cyclic-MEKP-1 cyclic methyl-ethyl-ketone peroxide (41 % w/w in Isopar M) ex Akzo Nobel 93% trimeric, 7% dimeric compounds (GC
area%) Cyclic-MEKP-2 cyclic methyl-ethyl-ketone peroxide (29.7% w/w in Diesel 1 ) ex Akzo Nobel 85% trimeric, 15% dimeric compounds (GC
10 area%) 2-EHN 2-ethylhexyl nitrate (97%) ex Aldrich Trigonox~ B di-tert-butyl peroxide ex Akzo Nobel DF-0 Low sulfur Diesel #2 ex Octel with a boiling range of 163-370°C, a flash point of 51.6-65.5°C (D-93), and an auto- , ignition temperature of 257°C (E-659).
Procedure The performance of ignition improvers in the process according to the invention was evaluated by means of the following screening method:
~ mixing the ignition improver in the specified amount with the diesel fuel at room temperature, ~ injecting a sample of 100 ~I or 250 wl by means of a syringe into an apparatus according to DIN 51794, which is controlled at a temperature of 270°C, and measuring the time that elapses before the sample ignites.
Alternatively, the cetane number of the fuel is measured according to method ASTM D-613.
Procedure The performance of ignition improvers in the process according to the invention was evaluated by means of the following screening method:
~ mixing the ignition improver in the specified amount with the diesel fuel at room temperature, ~ injecting a sample of 100 ~I or 250 wl by means of a syringe into an apparatus according to DIN 51794, which is controlled at a temperature of 270°C, and measuring the time that elapses before the sample ignites.
Alternatively, the cetane number of the fuel is measured according to method ASTM D-613.
The active oxygen content of the peroxides and fuels was analyzed by means of conventional analytical techniques such as iodometric titration and gas chromatographic analysis. More specifically, linear ketone peroxides were analyzed by means of method Jo/97.3 and the total amount of active oxygen was analyzed by means of method Jo/97.2. The ratio of dimeric to trimeric ketone peroxide was analyzed by means of method GC 97.8. These methods are available upon request from Akzo Nobel.
Predominantly trimeric cyclic methyiisobutyl ketone peroxide to be used as a fuel additive was produced by adding 97.1 g of hydrogen peroxide (70%) to a stirred mixture of 200 g of methylisobutyl ketone, 100 g of Isopar~ M, and 196 g of sulfuric acid (50%) over a period of 20 minutes, under a temperature of 25°C. The mixture was then stirred for another 3 hours at 40°C
and for 18 hours at 30°C. The organic phase was separated, washed with water and caustic and sulfite solutions, respectively, and dried over magnesium sulfate dehydrate. This process resulted in 235 g of an organic liquid with a total active oxygen content of 2.14%, of which 2.07% was cyclic methylisobutyl ketone peroxide and less than 0.07% was linear methylisobutyl ketone peroxide. The ratio of dimeric to trimeric cyclic compounds was 12:88 GC area%.
Example 1 Diesel fuel DFO was mixed with sufficient cyclic-MEKP-1 to give a 1 % w/w concentration of cyclic ketone peroxide in the diesel fuel.
Both the 100 ~,I and the 250 ~I sample, when tested as described above, ignited after 3.0 seconds. The cetane number of the ignition improved fuel was greater than 73.7.
Predominantly trimeric cyclic methyiisobutyl ketone peroxide to be used as a fuel additive was produced by adding 97.1 g of hydrogen peroxide (70%) to a stirred mixture of 200 g of methylisobutyl ketone, 100 g of Isopar~ M, and 196 g of sulfuric acid (50%) over a period of 20 minutes, under a temperature of 25°C. The mixture was then stirred for another 3 hours at 40°C
and for 18 hours at 30°C. The organic phase was separated, washed with water and caustic and sulfite solutions, respectively, and dried over magnesium sulfate dehydrate. This process resulted in 235 g of an organic liquid with a total active oxygen content of 2.14%, of which 2.07% was cyclic methylisobutyl ketone peroxide and less than 0.07% was linear methylisobutyl ketone peroxide. The ratio of dimeric to trimeric cyclic compounds was 12:88 GC area%.
Example 1 Diesel fuel DFO was mixed with sufficient cyclic-MEKP-1 to give a 1 % w/w concentration of cyclic ketone peroxide in the diesel fuel.
Both the 100 ~,I and the 250 ~I sample, when tested as described above, ignited after 3.0 seconds. The cetane number of the ignition improved fuel was greater than 73.7.
Comaarative Examples A-D
Example 1 was repeated, except that no or other conventional ignition improvers were used. The compounds used, their concentration in the diesel fuel, and the results of the tests are incorporated into the following table.
ComparativeIgnition ConcentrationTime Cetane Example improver in the fuel to Number ignition (s) A None 0 10.6 11.1 54.7 B 2-EHN 1 %w/w 2.8 2.7 70.9 C Trigonox 1 %w/w 1.1 1.2 69.7 B
D 2-EHN and 1 %w/w each 1.1 1.1 n.d.
Trigonox B
~ ~.u. - ~ m uCm~rnmea Example B was repeated using 0.787% w/w of 2-EHN and diesel 2. The ignition improved fuel (cetane number about 61 ) was evaluated according to Conradson test ASTM-D189. When converted to equivalent values for the Ramsbottom residue test, 0.2% w/w of carbon deposits was formed.
Comparative Examples E-G
The Examples 1, 3, and 5 of FR-862 974 were reworked as Comparative Examples E-G, respectively, except that Example 5 was not reworked in a continuous but in a discontinuous fashion.
The dissolution and performance of the cyclic acetone peroxide of Comparative Example E in fuel was unsatisfactory.
The cyclic butanone peroxides of Comparative Examples F and G contained 90 and 7fi% (GC area%) of dimeric butanone peroxide and 10 and 24% (GC
area%) of trimeric butanone peroxide, based on the GC area of cyclic ketone peroxides.
Example 1 was repeated, except that no or other conventional ignition improvers were used. The compounds used, their concentration in the diesel fuel, and the results of the tests are incorporated into the following table.
ComparativeIgnition ConcentrationTime Cetane Example improver in the fuel to Number ignition (s) A None 0 10.6 11.1 54.7 B 2-EHN 1 %w/w 2.8 2.7 70.9 C Trigonox 1 %w/w 1.1 1.2 69.7 B
D 2-EHN and 1 %w/w each 1.1 1.1 n.d.
Trigonox B
~ ~.u. - ~ m uCm~rnmea Example B was repeated using 0.787% w/w of 2-EHN and diesel 2. The ignition improved fuel (cetane number about 61 ) was evaluated according to Conradson test ASTM-D189. When converted to equivalent values for the Ramsbottom residue test, 0.2% w/w of carbon deposits was formed.
Comparative Examples E-G
The Examples 1, 3, and 5 of FR-862 974 were reworked as Comparative Examples E-G, respectively, except that Example 5 was not reworked in a continuous but in a discontinuous fashion.
The dissolution and performance of the cyclic acetone peroxide of Comparative Example E in fuel was unsatisfactory.
The cyclic butanone peroxides of Comparative Examples F and G contained 90 and 7fi% (GC area%) of dimeric butanone peroxide and 10 and 24% (GC
area%) of trimeric butanone peroxide, based on the GC area of cyclic ketone peroxides.
Examples 2-7 and Comparative Examples H J
Using three types of diesel fuel, various ketone peroxides were evaluated for their influence on the cetane number. In Examples 2-6 cyclic-MEKP-2 was used as an ignition fuel improver, while in Example 7 the cyclic methylisobutyl ketone peroxide as prepared above was used. In Comparative Example H, no ketone peroxide was used, in Comparative Example 1 Butanox~M50 ex Akzo Nobel, a predominantly linear methylethyl ketone peroxide, was used, while in Comparative Example J, Trigonox~233 ex Akzo Nobel, a predominantly linear methylisobutyl ketone peroxide, was used.
Using three types of diesel fuel, various ketone peroxides were evaluated for their influence on the cetane number. In Examples 2-6 cyclic-MEKP-2 was used as an ignition fuel improver, while in Example 7 the cyclic methylisobutyl ketone peroxide as prepared above was used. In Comparative Example H, no ketone peroxide was used, in Comparative Example 1 Butanox~M50 ex Akzo Nobel, a predominantly linear methylethyl ketone peroxide, was used, while in Comparative Example J, Trigonox~233 ex Akzo Nobel, a predominantly linear methylisobutyl ketone peroxide, was used.
The diesel fuels that were used are characterized by the following:
Diesel 1 2 3 Supplied as Treated LGO Treated Treated LGO
LCO/LGO
mix Sulfur ppm 157 293 223 Density glml 0.8273 0.8505 0.8400 (at15C) Cetane index 58.83 49.36 57.87 Aromatic compounds Mono %w/w 22.7 36.3 25.0 Di %w/w 2.7 6.7 3.8 Tri %w/w 0.1 0.5 0.2 Saturates %w/w 74.5 56.5 71.0 Sim Dist (ASTM
D-2887) IBP C 125.4 120.2 134.2 10% C 206.9 201.4 235.3 20% 233.0 227.1 263.1 30% 252.7 246.1 280.7 40 C 269.9 262.1 295.7 50 C 286.6 278.2 309.6 60 C 302.3 294.9 324.1 70 C 318.1 311.4 341.6 80 C 338.7 330.6 360.2 90 C 365.5 356.3 385.7 FBP C 427.1 425.8 450.9 LGO = light gas oil LCO = light cycling oil The following results were obtained:
Example Peroxide Cetane number %w/w Type Diesel1 Diesel2 Diesel3 2 0.0596 Cyclic MEKP 61.5 49.5 60.4 3 0.179 Cyclic MEKP 65.0 52.5 65.3 4 0.298 Cyclic MEKP 66.1 56.7 66.1 5 0.447 Cyclic MEKP 70.6 59.0 69.9 6 0.596 Cyclic MEKP 73.5 61.4 74.0 7 0.397 Cyclic MiBKPn.d. n.d. 67.0 H 0 None 58:9 46.7 57.8 I 0.200 Linear MEKP n.d. 49.6 n.d.
J 0.293 Linear MiBKPn.d. 51.0 n.d.
n.d. = not determined Obviously, on an equal active oxygen basis, the cyclic ketone peroxides of the higher ketones are more efficient at improving the cetane number.
Also, the product of Example 6 in diesel 2 was evaluated according to Conradson test ASTM-D189. When converted to equivalent values for the Ramsbottom residue test, 0.05% w/w of carbon deposits was formed, which is much better than the result obtained in Comparative Example B.
Example 8 A fuel according to the invention was prepared by adding 19.4 g of hydrogen peroxide to a stirred mixture of 27 g of diesel 1, 28.8 g of methylethyl ketone peroxide, and 14.0 g of sulfuric acid over a period of 20 minutes, while maintaining a temperature of about 20°C. The mixture was then stirred for another 90 minutes at 20°C, and the two layers were separated. The organic layer was washed with 25 g of a 6% w/w solution of sodium hydrogen carbonate, dried over magnesium sulfate dihydrate, and filtered. The product contained predominantly cyclic methylethyl ketone peroxide with a ratio of dimericltrimeric compounds of 13:87 GC area%.
Example 9 and Comparative Example K.
In order to demonstrate the differences in effect of dimeric and trimeric cyclic ketone peroxides when used as a fuel ignition improver, a diesel fuel was doped with 0.595% w/w of cyclic methylethyl ketone peroxide. In Example 9, a product was used with a ratio of dimeric/trimeric compounds of 5.6:94.4 (GC
area%), while in Comparative Example K this ratio was 98.6:1.4 (GC area%).
The cetane number of the untreated fuel was 54.7.
The cetane number of the fuel of Example 9 was 69.3.
The cetane number of the fuels of Comparative Example K was 64.7.
Diesel 1 2 3 Supplied as Treated LGO Treated Treated LGO
LCO/LGO
mix Sulfur ppm 157 293 223 Density glml 0.8273 0.8505 0.8400 (at15C) Cetane index 58.83 49.36 57.87 Aromatic compounds Mono %w/w 22.7 36.3 25.0 Di %w/w 2.7 6.7 3.8 Tri %w/w 0.1 0.5 0.2 Saturates %w/w 74.5 56.5 71.0 Sim Dist (ASTM
D-2887) IBP C 125.4 120.2 134.2 10% C 206.9 201.4 235.3 20% 233.0 227.1 263.1 30% 252.7 246.1 280.7 40 C 269.9 262.1 295.7 50 C 286.6 278.2 309.6 60 C 302.3 294.9 324.1 70 C 318.1 311.4 341.6 80 C 338.7 330.6 360.2 90 C 365.5 356.3 385.7 FBP C 427.1 425.8 450.9 LGO = light gas oil LCO = light cycling oil The following results were obtained:
Example Peroxide Cetane number %w/w Type Diesel1 Diesel2 Diesel3 2 0.0596 Cyclic MEKP 61.5 49.5 60.4 3 0.179 Cyclic MEKP 65.0 52.5 65.3 4 0.298 Cyclic MEKP 66.1 56.7 66.1 5 0.447 Cyclic MEKP 70.6 59.0 69.9 6 0.596 Cyclic MEKP 73.5 61.4 74.0 7 0.397 Cyclic MiBKPn.d. n.d. 67.0 H 0 None 58:9 46.7 57.8 I 0.200 Linear MEKP n.d. 49.6 n.d.
J 0.293 Linear MiBKPn.d. 51.0 n.d.
n.d. = not determined Obviously, on an equal active oxygen basis, the cyclic ketone peroxides of the higher ketones are more efficient at improving the cetane number.
Also, the product of Example 6 in diesel 2 was evaluated according to Conradson test ASTM-D189. When converted to equivalent values for the Ramsbottom residue test, 0.05% w/w of carbon deposits was formed, which is much better than the result obtained in Comparative Example B.
Example 8 A fuel according to the invention was prepared by adding 19.4 g of hydrogen peroxide to a stirred mixture of 27 g of diesel 1, 28.8 g of methylethyl ketone peroxide, and 14.0 g of sulfuric acid over a period of 20 minutes, while maintaining a temperature of about 20°C. The mixture was then stirred for another 90 minutes at 20°C, and the two layers were separated. The organic layer was washed with 25 g of a 6% w/w solution of sodium hydrogen carbonate, dried over magnesium sulfate dihydrate, and filtered. The product contained predominantly cyclic methylethyl ketone peroxide with a ratio of dimericltrimeric compounds of 13:87 GC area%.
Example 9 and Comparative Example K.
In order to demonstrate the differences in effect of dimeric and trimeric cyclic ketone peroxides when used as a fuel ignition improver, a diesel fuel was doped with 0.595% w/w of cyclic methylethyl ketone peroxide. In Example 9, a product was used with a ratio of dimeric/trimeric compounds of 5.6:94.4 (GC
area%), while in Comparative Example K this ratio was 98.6:1.4 (GC area%).
The cetane number of the untreated fuel was 54.7.
The cetane number of the fuel of Example 9 was 69.3.
The cetane number of the fuels of Comparative Example K was 64.7.
Claims (13)
1. Fuel with improved ignition characteristics comprising one or more cyclic ketone peroxides, characterized in that it comprises from 0.01 to 10 percent by weight of one or more cyclic ketone peroxides selected from the group of peroxides represented by formula I:
wherein R1, R3, and R5 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, which groups may include linear or branched alkyl moieties; R2, R4, and R6 are independently selected from the group consisting of hydrogen, C2-C20 alkyl, C3-C20 cycloalkyl, C8-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, which groups may include linear or branched alkyl moieties; and each of R1-R6 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrite, and amido, with the proviso that said peroxides make up at least 35% by weight of all cyclic ketone peroxides in the fuel.
wherein R1, R3, and R5 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, which groups may include linear or branched alkyl moieties; R2, R4, and R6 are independently selected from the group consisting of hydrogen, C2-C20 alkyl, C3-C20 cycloalkyl, C8-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, which groups may include linear or branched alkyl moieties; and each of R1-R6 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, ester, carboxy, nitrite, and amido, with the proviso that said peroxides make up at least 35% by weight of all cyclic ketone peroxides in the fuel.
2. A fuel according to claim 1, characterized in that the final concentration of the peroxide(s) according to formula I in the fuel is between 0.025 and 5 percent by weight, based on the weight of the total formulation.
3. A fuel according to claim 1 or 2, characterized in that at least one of the cyclic ketone peroxides in the fuel is derived from one or more ketoses selected from the group consisting of acetone, methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, isomers of these ketones, and mixtures thereof.
4. A fuel according to claim 3, characterized in that it comprises a cyclic ketone peroxide of formula I derived from at least one ketone selected from the group consisting of methyl-n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, and isomers thereof.
5. A fuel according to claim 4, characterized in that the cyclic ketone peroxide of formula I is derived from one ketone selected from the group consisting of methylbutyl ketone, methyl-n-amyl ketone, ethytbutyl ketone, ethylpropyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, methylpropyl ketone, diethyl ketone, methylethyl ketone, and isomers thereof.
6. A fuel according to any one of claims 1-5, characterized in that the amount of cyclic ketone peroxide of formula I in the fuel is at least 40% by weight, preferably at least 50% by weight, and most preferably more than 80% by weight, based on the weight of all cyclic ketone peroxide in the fuel.
7. A fuel according to any one of claims 1-6, characterized in that the cyclic ketone peroxide of formula I is selected from the group consisting of cyclic methylethyl ketone peroxide, cyclic methylisobutyl ketone peroxide, and cyclic methylisopropyl ketone peroxide.
8. A fuel according to any one of claims 1-7, characterized in that the fuel is a diesel fuel.
9. Process to make an ignition improved fuel according to any one of claims 1-8, characterized in that a cyclic ketone peroxide composition is combined with a fuel, which cyclic ketone peroxide composition comprises at least 35% by weight, based on the weight of all cyclic ketone peroxides, of one or more cyclic ketone peroxides selected from peroxides represented by formula I and further comprises one or more non-halogenated phlegmatizers selected from the group consisting of hydrocarbons, oxygenated hydrocarbons, alkyl nitrates, and mixtures thereof.
10. A process according to claim 9 wherein a phlegmatizer is used that is selected from the group consisting of alkanols, cycloalkanols, alkylene glycols, alkylene glycol monoalkyl ethers, ethers, aldehydes, ketones, epoxides, esters, hydrocarbons, and mixtures thereof.
11. A process according to claim 10 wherein the phlegmatizer is selected from ethers or hydrocarbons, preferably from hydrocarbon fuels, such as diesel fuels.
12. A process to make an ignition improved fuel according to any one of claims 1-8, characterized in that the cyclic ketone peroxide is produced in the specified concentration in the fuel.
13. Use of a fuel according to any one of claims 1-8 in a combustion engine to reduce the emission of pollutants.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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EP97204051 | 1997-12-22 | ||
EP97204051.3 | 1997-12-22 | ||
US7205098P | 1998-01-21 | 1998-01-21 | |
US60/072,050 | 1998-01-21 | ||
PCT/EP1998/008131 WO1999032584A1 (en) | 1997-12-22 | 1998-12-14 | Ignition improved fuels |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2315683A1 true CA2315683A1 (en) | 1999-07-01 |
Family
ID=8229100
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002315683A Abandoned CA2315683A1 (en) | 1997-12-22 | 1998-12-14 | Ignition improved fuels |
Country Status (13)
Country | Link |
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EP (1) | EP1042433A1 (en) |
JP (1) | JP2001527124A (en) |
CN (1) | CN1121479C (en) |
AU (1) | AU2271399A (en) |
BR (1) | BR9814373A (en) |
CA (1) | CA2315683A1 (en) |
HU (1) | HUP0100654A2 (en) |
ID (1) | ID25464A (en) |
NZ (1) | NZ505170A (en) |
PL (1) | PL341331A1 (en) |
TR (1) | TR200001920T2 (en) |
WO (1) | WO1999032584A1 (en) |
ZA (1) | ZA9811722B (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2001293756A1 (en) * | 2000-08-15 | 2002-02-25 | Akzo Nobel N.V. | Use of trioxepans in ignition improved fuels |
WO2004072059A1 (en) * | 2003-02-13 | 2004-08-26 | Akzo Nobel N.V. | Storage stable cyclic ketone peroxide compositions |
EP1447404A1 (en) * | 2003-02-13 | 2004-08-18 | Akzo Nobel N.V. | Improved cyclic ketone peroxide compositions |
DE102009016492A1 (en) * | 2009-04-06 | 2010-10-14 | Bundesanstalt für Materialforschung und -Prüfung (BAM) | Fuel and use of the same |
EP2494009A1 (en) * | 2009-10-30 | 2012-09-05 | BP Corporation North America Inc. | Composition and method for reducing nox emissions from diesel engines at minimum fuel consumption |
DE102013112821A1 (en) | 2012-11-30 | 2014-06-05 | Shell Internationale Research Maatschappij B.V. | Fuel Compositions |
BR112015013896A2 (en) | 2012-12-21 | 2017-07-11 | Shell Int Research | liquid fuel composition, use of a compound, and methods for modifying the ignition delay and / or increasing the cetane number and / or modifying the burning period of a diesel fuel composition, and for improving the energy output of an internal combustion engine |
WO2015059210A1 (en) | 2013-10-24 | 2015-04-30 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
US9587195B2 (en) | 2013-12-16 | 2017-03-07 | Shell Oil Company | Liquid composition |
PL3116865T3 (en) | 2014-03-11 | 2018-04-30 | Akzo Nobel Chemicals International B.V. | Cyclic ketone peroxide composition |
EP2949732B1 (en) | 2014-05-28 | 2018-06-20 | Shell International Research Maatschappij B.V. | Use of an oxanilide compound in a diesel fuel composition for the purpose of modifying the ignition delay and/or the burn period |
EP3088495A1 (en) * | 2015-04-28 | 2016-11-02 | United Initiators GmbH & Co. KG | Use of a fuel additive in diesel fuel for removing deposits in a diesel engine |
SG11201802774QA (en) | 2015-11-11 | 2018-05-30 | Shell Int Research | Process for preparing a diesel fuel composition |
CN106221834B (en) * | 2016-08-22 | 2018-01-26 | 天津市苏同兴盛环保科技有限公司 | Low-temperature methanol starts additive |
WO2018077976A1 (en) | 2016-10-27 | 2018-05-03 | Shell Internationale Research Maatschappij B.V. | Process for preparing an automotive gasoil |
WO2018206729A1 (en) | 2017-05-11 | 2018-11-15 | Shell Internationale Research Maatschappij B.V. | Process for preparing an automotive gas oil fraction |
CN112368359B (en) | 2018-07-02 | 2023-03-28 | 国际壳牌研究有限公司 | Liquid fuel composition |
IT202000020368A1 (en) * | 2020-08-24 | 2022-02-24 | Cesare Pedrazzini | ADDITIVE TO REDUCE THE PARTICULATE IN THE EMISSIONS DERIVING FROM THE COMBUSTION OF DIESEL AND FUEL OIL AND THE FUEL COMPOSITION THAT CONTAINS THEM |
CN114686278A (en) * | 2022-02-18 | 2022-07-01 | 任国辉 | Use of cyclic peroxides in petroleum products |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE617492C (en) * | 1934-05-26 | 1935-08-20 | Bataafsche Petroleum | Process for the production of fuel oil for diesel and semi-diesel engines |
FR862070A (en) * | 1938-12-02 | 1941-02-26 | Bataafsche Petroleum | Process for the preparation of heteropolymeric aliphatic ketone peroxides and liquid fuels containing these peroxides |
FR862974A (en) * | 1940-01-18 | 1941-03-20 | Bataafsche Petroleum | Process for the preparation of peroxides of aliphatic ketones and liquid fuels having improved ignition quality |
US3003000A (en) * | 1959-07-01 | 1961-10-03 | Research Corp | Organic peroxides |
US3116300A (en) * | 1960-11-18 | 1963-12-31 | Pure Oil Co | Process for preparing dicyclo-alkylidene diperoxides |
US5808110A (en) * | 1994-07-21 | 1998-09-15 | Akzo Nobel Nv | Cyclic ketone peroxide formulations |
-
1998
- 1998-12-14 JP JP2000525509A patent/JP2001527124A/en active Pending
- 1998-12-14 HU HU0100654A patent/HUP0100654A2/en unknown
- 1998-12-14 WO PCT/EP1998/008131 patent/WO1999032584A1/en not_active Application Discontinuation
- 1998-12-14 CA CA002315683A patent/CA2315683A1/en not_active Abandoned
- 1998-12-14 CN CN98812578A patent/CN1121479C/en not_active Expired - Fee Related
- 1998-12-14 EP EP98966311A patent/EP1042433A1/en not_active Ceased
- 1998-12-14 AU AU22713/99A patent/AU2271399A/en not_active Abandoned
- 1998-12-14 NZ NZ505170A patent/NZ505170A/en unknown
- 1998-12-14 PL PL98341331A patent/PL341331A1/en unknown
- 1998-12-14 BR BR9814373-5A patent/BR9814373A/en not_active IP Right Cessation
- 1998-12-14 TR TR2000/01920T patent/TR200001920T2/en unknown
- 1998-12-14 ID IDW20001206A patent/ID25464A/en unknown
- 1998-12-21 ZA ZA9811722A patent/ZA9811722B/en unknown
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NZ505170A (en) | 2002-02-01 |
JP2001527124A (en) | 2001-12-25 |
PL341331A1 (en) | 2001-04-09 |
EP1042433A1 (en) | 2000-10-11 |
BR9814373A (en) | 2000-10-10 |
AU2271399A (en) | 1999-07-12 |
TR200001920T2 (en) | 2000-12-21 |
ID25464A (en) | 2000-10-05 |
CN1283218A (en) | 2001-02-07 |
WO1999032584A1 (en) | 1999-07-01 |
CN1121479C (en) | 2003-09-17 |
ZA9811722B (en) | 1999-06-21 |
HUP0100654A2 (en) | 2001-06-28 |
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