CN1283218A - 着火性能改善的燃烧 - Google Patents
着火性能改善的燃烧 Download PDFInfo
- Publication number
- CN1283218A CN1283218A CN98812578A CN98812578A CN1283218A CN 1283218 A CN1283218 A CN 1283218A CN 98812578 A CN98812578 A CN 98812578A CN 98812578 A CN98812578 A CN 98812578A CN 1283218 A CN1283218 A CN 1283218A
- Authority
- CN
- China
- Prior art keywords
- ketone
- fuel
- methyl
- cyclic
- ethyl
- 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.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 117
- -1 cyclic ketone peroxide Chemical class 0.000 claims abstract description 102
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 38
- 239000002283 diesel fuel Substances 0.000 claims description 30
- 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 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 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
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 claims description 6
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 6
- ZICCKEFQTCBFAO-UHFFFAOYSA-N 1-cyclohexylbutan-2-one Chemical compound CCC(=O)CC1CCCCC1 ZICCKEFQTCBFAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 5
- MYBWBOAMPZHRQX-UHFFFAOYSA-N 1-cyclohexyl-4-methylpentan-2-one Chemical compound CC(C)CC(=O)CC1CCCCC1 MYBWBOAMPZHRQX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 claims 1
- IWPWMAJDSLSRIP-UHFFFAOYSA-N nezukone Chemical compound CC(C)C1=CC=CC(=O)C=C1 IWPWMAJDSLSRIP-UHFFFAOYSA-N 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 16
- 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
- 239000012190 activator Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 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 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 8
- 238000006471 dimerization reaction Methods 0.000 description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000005829 trimerization reaction Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229940032007 methylethyl ketone Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- IDNUEBSJWINEMI-UHFFFAOYSA-N ethyl nitrate Chemical compound CCO[N+]([O-])=O IDNUEBSJWINEMI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil 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
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
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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
-
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
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Abstract
介绍了一种燃料,用0.01-10%w/w的环酮过氧化物掺杂,其特征为含有0.01-10%w/w的分子式Ⅰ的环酮过氧化物,其中R1-R6分别选自由氢,C1-C20烷基,C3-C20环烷基,C6-C20芳基,C7-C20芳烷基,C7-C20烷芳基组成的组,该基团可带线性或支化烷基部分;R1-R6中每一个都可任意被选自羟基,烷氧基,线性或支化烷基,芳氧基,酯,羧基,腈基和酰氨基的一个或多个基团取代,只要燃料中上述过氧化物至少占所有过氧化物的重量的35%,以减少燃料用于燃油发动机中时排放的污染物,同时还介绍了制备这种燃料的工艺。
Description
本发明涉及由一种或多种酮过氧化物组成的着火性能改善的燃料,还涉及了这种燃料的制备工艺。
燃料中使用过氧化物早已是常识。回顾在二十世纪四十年代就有US 2,378,341中提出,使用带有至少一个脂肪族叔碳原子的烃的过氧化物,其中所述过氧化物的过氧基连接两个叔碳原子,同时,Ind.Eng.Chem.,Vol.41,No.8,1679-1682页中指出,使用二叔丁基过氧化物和2,2-二(叔丁基过氧基)丁烷可以改善柴油燃料的着火性能。还有FR-B-862,070揭示了一种在不希望的低温下从脂肪族酮的混合物中制备合聚酮过氧化物的危险工艺以及它们在燃料中的用途。据说所得产物在燃料中的溶解性得到了改善并具有低的结晶温度。
FR-B-862,974中描述了某种环酮过氧化物的生产和它们在柴油中使用以改善着火特性方面的用途。
1961年US 3,003,000中描述了酮过氧化物,低聚酮过氧化物,生产它们的工艺以及它们在特别是柴油燃料中的一般用途。该工艺中也产生了一些环酮过氧化物副产物。这些副产物在低聚酮过氧化物中只有痕量。在柴油燃料配制物中的用途还没有加以说明。
US 3,116,300(1963年发表)描述了二聚环酮过氧化物,即两分子酮反应得到的产物。
着火性能改善剂用于因着火性而不可作燃油发动机的燃料的烃类馏份和含有残余物的油。通常情况下这些燃料因着火滞后太久而受限制,所谓的着火滞后即是在将燃料注入例如柴油发动机一类的直接注入型发动机中的燃烧区和燃料着火时刻之间的时间,或外部引燃源的活化,例如火花塞,和燃料着火时刻之间的时间。结果发现燃烧效率差,发动机操作困难,附带所有不利的后果。所以,术语改善的着火性能是指在燃油发动机中燃料的燃烧效率改善,通常可从燃料的较高的十六烷值和上述发动机中燃料燃烧排放的污染物减少而明显看出。众所周知,使用着火性能改善的柴油可减少烃类,一氧化碳和NOx以及微尘物(油烟)的排放,根据燃料的类型和所用的着火性能改善剂的类型和数量,上述排放量减少40%是完全可行的。
尽管酮过氧化物已发明出来了一段时间,但是还没有发现它们作为着火性能改善剂的工业用途。相反,现在使用的改善(柴油)燃料的着火性能的工业产品是二叔丁基过氧化物和2-乙基己基硝酸酯,参见Chemtech,8-97,第38-41页。但是,这些产品有各种缺点。硝酸酯在燃烧时可能产生NOx,而二叔丁基过氧化物闪点低,挥发性高,会导致各种安全上的隐患。大多数过氧化物在柴油燃料中也不具有长期(热)稳定性。特别是在例如燃料体系中可能遇到的较高温度下,热稳定性降低会产生胶状物或导致燃料的其它降解。同时,过氧化物的分解产物一般具有(部分)醇的特征,这会增加不希望的燃料吸收的水。而且,迄今使用的大部分过氧化物都具有较低的活性物质含量。还有,大部分过氧化物的价格/性能比也妨碍了将它们广泛引入(柴油)燃料中。在这方面已注意到例如FR-B-862,974中指出,二聚环酮过氧化物性能不令人满意,因而认为不能接受这些产品的价格/性能比。况切,传统的环酮过氧化物的二聚结构因这种产品的挥发性和低闪点还可能存在安全隐患。总之,仍然需要改善性能的燃料。
令人惊喜的是,WO 96/03397中公开的一些过氧化物组合物被发现非常适合于改善燃料的着火性能。WO 96/03397涉及大量环酮过氧化物的配制物,如下所述,由各种烟火添加剂组成。但是此专利申请并未指出或建议在燃料中使用环酮过氧化物。将WO 96/03397中性能好的环酮过氧化物和例如FR-B-862,974中的环酮过氧化物相比较可以看出,令人惊喜的性能和所用的环酮过氧化物的性质有关。因此,本发明归属于恰当选择环酮过氧化物来改善燃料。
本发明的燃料的特征在于含有0.001~10wt.%的一种或多种选自分子式Ⅰ所代表的一类过氧化物的环酮过氧化物:其中R1,R3和R5分别选自由氢,C1-C20烷基,C3-C20环烷基,C6-C20芳基,C7-C20芳烷基和C7-C20烷芳基组成的组,这些可包括线性或支化烷基部分的基团,R2,R4和R6分别选自由氢,C2-C20烷基,C3-C20环烷基,C6-C20芳基,C7-C20芳烷基和C7-C20烷芳基组成的组,这基团可包括线性或支化烷基部分;R1-R6中每一个都可任选被选自羟基,烷氧基,线性或支化烷基,芳氧基,酯基,羧基,腈基和酰氨基中的一个或多个基团取代,只要燃料中上述过氧化物至少占所有环酮过氧化物的35%重量。
按本发明的改善燃料不具有大部分上述缺点。更特别的是发现使用分子式Ⅰ的环酮过氧化物得到了具有特别优良的性能的燃料,这些性能有关着火时间和相关的十六烷值方面,良好的溶混性,良好的化学稳定性,也就是抗氧,酸和金属氧化物(例如生锈)的性能,与燃料体系中的其它组分,例如金属,橡胶配件,垫圈和软管等有良好的相容性。
按本发明的环酮过氧化物优选含有氧,碳和氢原子,以避免它们所在的燃料燃烧时放出N0x所产生的不利的影响。更优选按分子式Ⅰ的环酮过氧化物是由至少一种分子量大于丙酮的酮衍生而来,从而分子中碳原子总数大于6。使用这些高分子量的酮对上述环酮过氧化物在燃料中的溶解性有积极的作用,并发现基于加入的活泼氧的数量是更有效的着火性能改善剂。优选使用至少4个碳原子的酮,更优选至少5个碳原子的酮来制备本发明的环酮过氧化物。同时,按本发明的环酮过氧化物中碳原子总数优选少于40,更优选少于30,最优选少于25。否则,分子量会太高,会要求加入燃料中高剂量的过氧化物,这在经济上是不吸引人的。偶然发现,如果使用含有丙酮的酮的混合物,那么会产生不希望的二聚和三聚丙酮过氧化物。这种环丙酮过氧化物当用在燃料,特别是柴油燃料中时可能在低温下产生沉淀,那么可能要求进一步提纯。因此酮混合物中不要使用丙酮。而且,虽然可使用酮混合物制备本发明的环酮过氧化物,但是优选使用仅仅一种酮,因而R1=R3=R5和R2=R4=R6。也就是,这种环酮过氧化物更容易制备,不易因改变工艺条件而改变组成。所以,这样形成的着火性能改善剂的质量更容易控制。
改善着火时间的环酮过氧化物优选的含量是使得在下述的模型试验中,处理过的燃料的自燃时间比未处理过的燃料的自燃时间短。更优选在上述试验中270℃下自燃时间减少量大于10%。特别优选,在此试验温度下自燃时间减少量大于25%。最优选在270℃下自燃时间减少至少50%。
优选,按分子式I的一种或多种环酮过氧化物在最终的燃料配制物中含量为0.025~5%w/w。最优选,燃料中分子式I的环酮过氧化物含量为0.05-2.5%w/w。含量较低的过氧化物不会明显改善燃料的着火性能,而含量较高证明可能会不安全或不经济。
贯穿本文所用的术语燃料指包括用于燃油发动机的所有烃类馏份和含残渣的油,它们在石油的煤油馏份和润滑油馏份之间蒸馏出。这种燃料中可含有通常的添加剂,例如消泡剂,喷嘴清洁剂,干燥剂,浊点抑制剂,也称作抗凝胶剂,藻的控制剂,润滑油,染料和阻氧化剂,但也可含有其它的改善着火性能或改善燃烧的添加剂,只要这些添加剂不会对本发明的最终燃料组合物的贮存稳定性产生不利的影响。优选的燃料是柴油燃料。
第二个实施方案中,本发明涉及制备着火性能改善的燃料的工艺。为此,合适的环酮过氧化物组合物与一种燃料相结合,否则环酮过氧化物直接在上述燃料中制备。
环酮过氧化物的制备参见WO 96/03397。它指出如何通过改变反应条件来控制所得的环酮过氧化物的组成。按分子式Ⅰ的三聚环酮过氧化物优选在温和的条件下制备,例如通过降低工艺中酸的用量,降低温度,反应短时间,和/或同时计量过氧化氢和酸。而且,三聚化合物的制备在反应中使用较少水量时有利,可能因为有较少量的三聚化合物水解生成二聚化合物。恰当的条件取决于所用的酮的种类和各种反应物的浓度。但是专业人员会很容易确定选择制备本发明用的环酮过氧化物的工艺条件。但是优选工艺温度范围为0-80℃,更优选5-60℃,最优选20-45℃,以实现有效成本的工艺。
合成本发明使用的环酮过氧化物所使用的合适的酮,例如丙酮,苯乙酮,甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基异戊基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,二甲基酮,二乙基酮,二丙基酮,甲基乙基酮,甲基异丁基酮,甲基异丙基酮,甲基丙基酮,甲基叔丁基酮,异丁基庚基酮,二异丁基酮,2,4-戊二酮,2,4-己二酮,2,4-庚二酮,3,5-庚二酮,3,5-辛二酮,5-甲基-2,4-己二酮,2,6-二甲基-3,5-庚二酮,2,4-辛二酮,5,5-二甲基-2,4-己二酮,6-甲基-2,4-庚二酮,1-苯基-1,3-丁二酮,1-苯基-1,3-戊二酮,1,3-二苯基-1,3-丙二酮,1-苯基-2,4-戊二酮,甲基苄基酮,苯基甲基酮,苯基乙基酮和它们的偶联产物。当然,也可使用其它相应于分子式I的过氧化物中有合适的R基团的酮,以及两种或多种不同酮的混合物。
按本发明优选使用的分子式Ⅰ的过氧化物例如,由甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,甲基丙基酮,二乙基酮,甲基乙基酮,这些酮的异构体,以及它们的混合物衍生而来的环酮过氧化物。更优选的分子式Ⅰ的过氧化物是基于至少一种选自甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,甲基丙基酮,二乙基酮,甲基乙基酮,和这些酮的一种或多种异构体,例如甲基异丁基酮和甲基异丙基酮等中的酮。
这些过氧化物可以任意固体或液体形式制备,运输,储存和应用,但优选在非卤化液态烟火添加剂中的溶液形式。然后这些组合物可以与燃料相结合。应当注意某些烟火添加剂可能不适于用于所有本发明的酮过氧化物组合物。更特别注意的是,为获得一种安全的组合物,烟火添加剂应当具有相对酮过氧化物的分解温度的某一最低闪点和最低沸点,以使得不会让烟火添加剂蒸发而留下浓缩的不安全的酮过氧化物组合物。
优选的烟火添加剂选自由烃,例如(柴油)燃料,石蜡油和轻油,氧化烃,例如醚,醛,环氧化物,酯,酮,醇和有机过氧化物,例如线性酮过氧化物和二叔丁基过氧化物,硝酸烷基酯,例如2-乙基己基硝酸酯,以及它们的混合物组成的组。优选的用于环酮过氧化物的液态烟火添加剂的例子有醇,特别是高级脂肪醇,环醇,烷二醇,烷二醇单烷基醚,醚,特别是甲基叔丁基醚,醛,酮,环氧化物,酯,烃类溶剂,包括甲苯,二甲苯,(柴油)燃料,石蜡油,和轻油。更优选的液态烟火添加剂是醚和烃。最优选用燃料作烟火添加剂。浓的环酮过氧化物组合物非常适于用燃料进一步稀释以获得含有改善着火性能剂量的上述过氧化物的燃料。
按本发明的燃料可以只含有分子式I的过氧化物作为着火性能改善剂。但是它们也可以结合其它的着火性能改善剂,例如传统的二叔丁基过氧化物和/或2-乙基己基硝酸酯。如果分子式Ⅰ的过氧化物和其它环酮过氧化物着火性能改善剂一起使用,那么它们占燃料中的所有环酮过氧化物重量的百分比优选为至少40%w/w,更优选至少45%w/w,更优选至少50%w/w,再优选至少66%w/w,特别优选大于75%w/w。最优选的是按分子式I的环酮过氧化物占所有环酮过氧化物的80%w/w以上的组合物,因为它们能最有效地改善这些燃料的着火性能。如果燃料中只用基本上是二聚和三聚化合物(按分子式Ⅰ)的混合物组成的环酮过氧化物,那么已指出的优选范围表明,燃料中二聚化合物和三聚化合物的比值是低于约2∶1,更优选低于约3∶2,再优选低于约5∶4,再优选低于约1∶1,更优选低于1∶2,更优选低于约1∶3,最优选低于约1∶4。
为避免安全隐患,优选的用于构成申请的燃料的环酮过氧化物组合物基本上不是纯的环酮过氧化物。更优选的组合物含有占总配制物的低于99%w/w的环酮过氧化物,再优选低于90%w/w,特别优选低于85%w/w。最优选,用于构成本发明的燃料的环酮过氧化物组合物含有占总组合物的低于75%w/w的环酮过氧化物。
还可以选择,环酮过氧化物在要改善着火性能的燃料中按要求的0.01~10%w/w的浓度制备。最后,传统的反应剂和催化剂也可引入未处理的燃料中进行反应。然后着火性能改善的燃料与污染物和生产用水分离出来,以传统的方法任意洗涤和干燥。这种制备过程中需要处理相当大量的水流,但是可以避免处理过氧化物浓缩物。
本发明由下述实施例进行阐述。
实施例所用材料Isopar_M Exxon Chemical公司的烃类烟火添加剂环状-MEKP-1 Akzo Nobel公司的环甲基乙基酮过氧化物(41%w/w的Isopar M溶液)93%三聚化合物,7%二聚化合物(GC中的面积百分比)环状-MEKP-2 Akzo Nobel公司的环甲基乙基酮过氧化物(29.7%w/w的柴油1溶液),85%三聚化合物,15%二聚化合物(GC中的面积百分比)2-EHN Aldrich公司的2-乙基己基硝酸酯(97%)Trigonox_B Akzo Nobel公司的二叔丁基过氧化物DF-o Octel公司的低硫柴油#2,沸程为163-370℃,闪点为51.6-65.5℃(D-93),自燃温度为257℃(E-659)。步骤
本发明工艺中着火性能改善剂的性能通过下面的屏蔽方法来评价:·室温下将着火性能改善剂和柴油燃料按指定量混合,·根据DIN51794,用注射器把100μl或250μl的样品注入恒定270℃的设备中,测定样品燃烧前经过的时间。
也可选择根据ASTM D-613方法测量燃料的十六烷值。
过氧化物和燃料中活泼氧的含量通过传统的分析技术,例如碘量滴定和气相色谱分析,来进行分析。更特殊的是,线性酮过氧化物用Jo/97.3方法分析,活泼氧的总量用Jo/97.2方法分析。二聚酮过氧化物和三聚酮过氧化物的比值用GC97.8方法分析。这些方法可从AkzoNobel公司申请得到。
制备用作燃料添加剂的主要是三聚环甲基异丁基酮过氧化物是在20-25℃下,将97.1g过氧化氢(70%)在20分钟内加入搅拌着的200g甲基异丁基酮,100g Isopar_M和196g硫酸(50%)的混合物中。然后混合物继续在40℃下搅拌3小时,在30℃下搅拌18小时。分离出有机相,分别用水,苛性碱溶液和亚硫酸盐溶液洗涤,用二水硫酸镁干燥。这一步得到235g具有活泼氧总量为2.14%的有机液体,其中有2.07%的环甲基异丁基酮过氧化物,低于0.07%的线性甲基异丁基酮过氧化物。二聚环酮化合物和三聚环酮化合物的比值是12∶88(GC面积百分比)。
实施例1
将柴油燃料DFO和足量的环状MEKP-1混合得到的柴油燃料含有1%w/w的环酮过氧化物。
100μl和250μl的样品在上述实验中都是3秒后燃烧。着火性能改善的燃料的十六烷值大于73.7。比较实施例A-D
重复实施例1,只是不用或改用其它的传统的着火性能改善剂。所用的化合物,它们在柴油燃料中的浓度和实验结果总结列入下表。
比较实施例 | 着火性能改善剂 | 燃料中浓度 | 开始燃烧时100μl | 间(s)250μl | 十六烷值 |
ABCD | 无2-EHNTrigonox B2-EHN和Trigonox B | 01%w/w1%w/w分别1%w/w | 10.62.81.11.1 | 11.12.71.21.1 | 54.770.969.7n.d. |
n.d.未测定
使用0.787%w/w的2-EHN和柴油2重复实施例B。根据Conradson实验ASTM-D189评价该着火性能改善的燃料(十六烷值约为61)。当转换为等价的Ramsbottom残余物实验时,产生0.2%w/w的碳沉积物。比较实施例E-G
比较实施例E-G分别重复FR-862974的实施例1,3和5,只是重复实施例5时不是连续方式而是间歇方式。
比较实施例E的环酮过氧化物在燃料中的溶解性和性能不令人满意。
比较实施例F和G的环丁酮过氧化物含有90%和76%(GC面积百分比)的二聚丁酮过氧化物,10%和24%(GC面积百分比)的三聚丁酮过氧化物,基于环酮过氧化物的GC面积。
实施例2-7和比较实施例H-J
用三类柴油燃料评价各种环酮过氧化物对十六烷值的影响。实施例2-6中使用环状MEKP-2作为着火燃料改善剂,而实施例7中用上述制备的环甲基异丁基酮过氧化物。比较实施例H中不用酮过氧化物,比较实施例I中用Akzo Nobel公司的Butanox_M50,一种主要为线性甲基乙基酮过氧化物,而比较实施例J中使用Akzo Nobel公司的Trigonox_233,一种主要为线性的甲基异丁基酮过氧化物。
所用柴油燃料的表征如下:
LGO代表轻粗柴油LCO代表轻循环油
柴油 | 1 | 2 | 3 | |
供应形式 | 已处理LGO | 已处理LCO/LGO混合物 | 已处理LGO | |
硫 | ppm | 157 | 293 | 223 |
密度(15℃) | g/ml | 0.8273 | 0.8505 | 0.8400 |
十六烷指数 | 58.83 | 49.36 | 57.87 | |
芳香化合物 | ||||
单 | %w/w | 22.7 | 36.3 | 25.0 |
二 | %w/w | 2.7 | 6.7 | 3.8 |
三 | %w/w | 0.1 | 0.5 | 0.2 |
饱和化合物 | %w/w | 74.5 | 56.5 | 71.0 |
Sim Dist(ASTM D-2887) | ||||
IBP | ℃ | 125.4 | 120.2 | 134.2 |
10% | ℃ | 206.9 | 201.4 | 235.3 |
20% | 233.0 | 227.1 | 263.1 | |
30% | 252.7 | 246.1 | 280.7 | |
40 | ℃ | 269.9 | 262.1 | 295.7 |
50 | ℃ | 286.6 | 278.2 | 309.6 |
60 | ℃ | 302.3 | 294.9 | 324.1 |
70 | ℃ | 318.1 | 311.4 | 341.6 |
80 | ℃ | 338.7 | 330.6 | 360.2 |
90 | ℃ | 365.5 | 356.3 | 385.7 |
FBP | ℃ | 427.1 | 425.8 | 450.9 |
下面是所得结果:
n.d.表示未测定
实施例 | 过氧化物 十六烷值 | ||||
%w/w | 类型 | 柴油1 | 柴油2 | 柴油3 | |
2 | 0.0596 | 环状MEKP | 61.5 | 49.5 | 60.4 |
3 | 0.179 | 环状MEKP | 65.0 | 52.5 | 65.3 |
4 | 0.298 | 环状MEKP | 66.1 | 56.7 | 66.1 |
5 | 0.447 | 环状MEKP | 70.6 | 59.0 | 69.9 |
6 | 0.596 | 环状MEKP | 73.5 | 61.4 | 74.0 |
7 | 0.397 | 环状MiBKP | n.d. | n.d. | 67.0 |
H | 0 | 无 | 58.9 | 46.7 | 57.8 |
I | 0.200 | 线性MEKP | n.d. | 49.6 | n.d. |
J | 0.293 | 线性MiBKP | n.d. | 51.0 | n.d. |
可明显看出,在等量活泼氧基础上,高级酮的环酮过氧化物对改善十六烷值更有效。
同时,根据Conradson实验ASTM-D189对柴油2中的实施例6的产物进行了评价。当转换为等价的Ramsbottom残余物实验时,产生0.05%w/w的碳沉积物,明显好于比较实施例B的结果。
实施例8
本发明的燃料的制备是将19.4g过氧化氢在20分钟内加入搅拌着的27g柴油1,28.8g甲基乙基酮过氧化物和14.0g硫酸的混合物中,同时温度恒定在约20℃。混合物继续在20℃下搅拌90分钟,将两层分离。有机层用25g 6%w/w的碳酸氢钠溶液洗,用二水硫酸镁干燥,然后过滤。产物中主要为环甲基乙基酮过氧化物,其中二聚化合物和三聚化合物的比为13∶87(GC面积百分比)。
实施例9和比较实施例K
为证明二聚和三聚环酮过氧化物用作燃料着火改善剂时效果的差别,柴油燃料中掺入0.595%w/w的环甲基乙基酮过氧化物。实施例9所用产品中二聚化合物和三聚化合物的比值为5.6∶94.4(GC面积百分比),而比较实施例K中的比值为98.6∶1.4(GC面积百分比)。
未处理的燃料的十六烷值为54.7。
实施例9的燃料的十六烷值为69.3。
对比实施例K的燃料的十六烷值是64.7。
Claims (13)
1.含有一种或多种环酮过氧化物的着火性能改善的燃料,其特征为含有0.01-10%w/w的一种或多种选自分子式Ⅰ代表的一类过氧化物的环酮过氧化物:
其中,R1,R3和R5分别选自由氢,C1-C20烷基,C3-C20环烷基,C6-C20芳基,C7-C20芳烷基和C7-C20烷芳基组成的组,这些基团可带线性或支化烷基部分;R2,R4和R6分别选自由氢,C2-C20烷基,C3-C20环烷基,C6-C20芳基,C7-C20芳烷基和C7-C20烷芳基组成的组,这些基团可带线性或支化烷基部分;R1-R6中每个都可任意被一个或多个选自羟基,烷氧基,线性或支化烷基,芳氧基,酯,羧基,腈基和酰氨基的基团取代,只要上述过氧化物至少占燃料中所有环酮过氧化物的35%w/w。
2.权利要求1的燃料,其特征为燃料中分子式Ⅰ的过氧化物的最终浓度是0.025-5%w/w,基于总配制物的重量。
3.权利要求1或2的燃料,其特征为燃料中至少一种环酮过氧化物是由选自由丙酮,甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,甲基丙基酮,二乙基酮,甲基乙基酮,这些酮的异构体和它们的混合物组成的组中的一种或多种酮衍生而来。
4.权利要求3的燃料,其特征为含有由至少一种选自由甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,甲基丙基酮,二乙基酮,甲基乙基酮和它们的异构体组成的组中的酮衍生而来的分子式I的环酮过氧化物。
5.权利要求4的燃料,其特征为分子式Ⅰ的环酮过氧化物由选自由甲基丁基酮,甲基正戊基酮,乙基丁基酮,乙基丙基酮,甲基庚基酮,甲基己基酮,乙基戊基酮,甲基丙基酮,二乙基酮,甲基乙基酮和它们的异构体组成的组中的一种酮衍生而来。
6.权利要求1-5中任一项的燃料,其特征为燃料中分子式Ⅰ的环酮过氧化物的含量至少为40%w/w,优选至少50%w/w,最优选大于80%w/w,基于燃料中所有环酮过氧化物。
7.权利要求1-6中任一项的燃料,其特征为分子式Ⅰ的环酮过氧化物选自由环甲基乙基酮过氧化物,环甲基异丁基酮过氧化物和环甲基异丙基酮过氧化物组成的组。
8.权利要求1-7中任一项的燃料,其特征为燃料是柴油燃料。
9.制备权利要求1-8中任一项的着火性能改善的燃料的工艺,其特征为,环酮过氧化物组合物与燃料相结合,该环酮过氧化物组合物含有至少占所有环酮过氧化物的35%w/w的选自分子式I代表的过氧化物的一种或多种环酮过氧化物,还含有选自烃,氧化烃,硝酸烷基酯及它们的混合物的一种或多种非卤化烟火添加剂。
10.权利要求9的工艺,其中所用的烟火添加剂选自烷醇,环烷醇,烷二醇,烷二醇单烷基醚,醚,醛,酮,环氧化物,酯,烃和它们的混合物。
11.权利要求10的工艺,其中烟火添加剂选自醚,或烃,优选自烃类燃料,例如柴油燃料。
12.制备权利要求1-8中任一项的着火性能改善的燃料的工艺,其特征为环酮过氧化物在燃料中以特定浓度制备。
13.权利要求1-8中任一项的燃料用在燃油发动机中来减少污染物的排放的用途。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100546988C (zh) * | 2003-02-13 | 2009-10-07 | 阿克佐诺贝尔股份有限公司 | 储存稳定的环状酮过氧化物组合物 |
CN106061957A (zh) * | 2014-03-11 | 2016-10-26 | 阿克苏诺贝尔化学品国际有限公司 | 环状酮过氧化物组合物 |
CN106221834A (zh) * | 2016-08-22 | 2016-12-14 | 天津市苏同兴盛环保科技有限公司 | 甲醇低温启动添加剂 |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1309667B1 (en) * | 2000-08-15 | 2004-10-20 | Akzo Nobel N.V. | Use of trioxepans in ignition improved fuels |
RU2351611C2 (ru) * | 2003-02-13 | 2009-04-10 | Акцо Нобель Н.В. | Стабильные при хранении композиции циклического пероксида кетона |
DE102009016492A1 (de) * | 2009-04-06 | 2010-10-14 | Bundesanstalt für Materialforschung und -Prüfung (BAM) | Brennstoff und Verwendung desselben |
AU2010313294A1 (en) | 2009-10-30 | 2012-05-31 | Bp Corporation North America Inc. | Composition and method for reducing NOx emissions from diesel engines at minimum fuel consumption |
DE102013112821A1 (de) | 2012-11-30 | 2014-06-05 | Shell Internationale Research Maatschappij B.V. | Kraftstoffzusammensetzungen |
BR112015013896A2 (pt) | 2012-12-21 | 2017-07-11 | Shell Int Research | composição de combustível líquida, uso de um composto, e, métodos para modificar o atraso de ignição e/ou aumentar o número de cetano e/ou modificar o período de queima de uma composição de combustível diesel, e para melhorar a saída de energia de um motor de combustão interna |
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EP3083905A1 (en) | 2013-12-16 | 2016-10-26 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
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SG11201802774QA (en) | 2015-11-11 | 2018-05-30 | Shell Int Research | Process for preparing a diesel fuel composition |
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 |
EP3818134B1 (en) | 2018-07-02 | 2023-02-22 | Shell Internationale Research Maatschappij B.V. | Liquid fuel compositions |
IT202000020368A1 (it) * | 2020-08-24 | 2022-02-24 | Cesare Pedrazzini | Additivo per ridurre il particolato nelle emissioni derivanti dalla combustione di gasolio ed olio combustibile e composizione carburante che lo contiene |
CN114686278A (zh) * | 2022-02-18 | 2022-07-01 | 任国辉 | 环状过氧化物在石油产品中的应用 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE617492C (de) * | 1934-05-26 | 1935-08-20 | Bataafsche Petroleum | Verfahren zur Herstellung eines Treiboeles fuer Diesel- und Halbdieselmaschinen |
FR862070A (fr) * | 1938-12-02 | 1941-02-26 | Bataafsche Petroleum | Procédé pour la préparation de peroxydes hétéropolymères de cétone aliphatique et de combustibles liquides contenant ces peroxydes |
FR862974A (fr) * | 1940-01-18 | 1941-03-20 | Bataafsche Petroleum | Procédé pour la préparation de péroxydes de cétones aliphatiques et de combustibles liquides ayant une qualité d'ignition améliorée |
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 |
HU216142B (hu) * | 1994-07-21 | 1999-04-28 | Akzo Nobel N.V. | Ciklusos keton-peroxidokat tartalmazó kompozíciók, és azok alkalmazása (ko)polimerek módosítására |
-
1998
- 1998-12-14 CA CA002315683A patent/CA2315683A1/en not_active Abandoned
- 1998-12-14 WO PCT/EP1998/008131 patent/WO1999032584A1/en not_active Application Discontinuation
- 1998-12-14 CN CN98812578A patent/CN1121479C/zh not_active Expired - Fee Related
- 1998-12-14 JP JP2000525509A patent/JP2001527124A/ja active Pending
- 1998-12-14 EP EP98966311A patent/EP1042433A1/en not_active Ceased
- 1998-12-14 PL PL98341331A patent/PL341331A1/xx unknown
- 1998-12-14 NZ NZ505170A patent/NZ505170A/en unknown
- 1998-12-14 BR BR9814373-5A patent/BR9814373A/pt not_active IP Right Cessation
- 1998-12-14 AU AU22713/99A patent/AU2271399A/en not_active Abandoned
- 1998-12-14 TR TR2000/01920T patent/TR200001920T2/xx unknown
- 1998-12-14 ID IDW20001206A patent/ID25464A/id unknown
- 1998-12-14 HU HU0100654A patent/HUP0100654A2/hu unknown
- 1998-12-21 ZA ZA9811722A patent/ZA9811722B/xx unknown
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100546988C (zh) * | 2003-02-13 | 2009-10-07 | 阿克佐诺贝尔股份有限公司 | 储存稳定的环状酮过氧化物组合物 |
CN106061957A (zh) * | 2014-03-11 | 2016-10-26 | 阿克苏诺贝尔化学品国际有限公司 | 环状酮过氧化物组合物 |
CN106061957B (zh) * | 2014-03-11 | 2018-11-02 | 阿克苏诺贝尔化学品国际有限公司 | 环状酮过氧化物组合物 |
CN106221834A (zh) * | 2016-08-22 | 2016-12-14 | 天津市苏同兴盛环保科技有限公司 | 甲醇低温启动添加剂 |
CN106221834B (zh) * | 2016-08-22 | 2018-01-26 | 天津市苏同兴盛环保科技有限公司 | 甲醇低温启动添加剂 |
Also Published As
Publication number | Publication date |
---|---|
AU2271399A (en) | 1999-07-12 |
TR200001920T2 (tr) | 2000-12-21 |
PL341331A1 (en) | 2001-04-09 |
CN1121479C (zh) | 2003-09-17 |
ID25464A (id) | 2000-10-05 |
JP2001527124A (ja) | 2001-12-25 |
WO1999032584A1 (en) | 1999-07-01 |
NZ505170A (en) | 2002-02-01 |
EP1042433A1 (en) | 2000-10-11 |
HUP0100654A2 (hu) | 2001-06-28 |
BR9814373A (pt) | 2000-10-10 |
CA2315683A1 (en) | 1999-07-01 |
ZA9811722B (en) | 1999-06-21 |
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