EP2361295A1 - Additifs anticalaminants sans azote pour carburant - Google Patents
Additifs anticalaminants sans azote pour carburantInfo
- Publication number
- EP2361295A1 EP2361295A1 EP09744556A EP09744556A EP2361295A1 EP 2361295 A1 EP2361295 A1 EP 2361295A1 EP 09744556 A EP09744556 A EP 09744556A EP 09744556 A EP09744556 A EP 09744556A EP 2361295 A1 EP2361295 A1 EP 2361295A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- group containing
- hydrocarbyl group
- fuel
- additive
- 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
- 239000002816 fuel additive Substances 0.000 title claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 70
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 35
- 239000000654 additive Substances 0.000 claims abstract description 121
- 239000000446 fuel Substances 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 106
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- 239000003599 detergent Substances 0.000 claims abstract description 52
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims description 76
- 239000001257 hydrogen Substances 0.000 claims description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims description 64
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 56
- 229920002367 Polyisobutene Polymers 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000006078 metal deactivator Substances 0.000 claims description 2
- -1 hydrocarbyl phenol Chemical compound 0.000 abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 9
- 229930003836 cresol Natural products 0.000 abstract description 6
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 22
- 150000002430 hydrocarbons Chemical class 0.000 description 22
- 239000004215 Carbon black (E152) Substances 0.000 description 21
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 229920000098 polyolefin Polymers 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 150000005673 monoalkenes Chemical class 0.000 description 6
- 239000003348 petrochemical agent Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000013020 final formulation Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical class CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 description 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 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical class CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002368 Glissopal ® Polymers 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 101100481912 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tpc-1 gene Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002382 heptanals Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JFNWATIZEGZGSY-UHFFFAOYSA-N n,n-diethylethanamine;trifluoroborane Chemical compound FB(F)F.CCN(CC)CC JFNWATIZEGZGSY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
-
- 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
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
-
- 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
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- 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
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- 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
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
Definitions
- the present invention relates to fuel additives, fuel additive compositions and fuel compositions as well as a method for fueling an internal combustion engine, providing improved deposit control inside the engine, as well as other benefits, with additives that are free of nitrogen.
- Hydrocarbon based fuels generally contain numerous deposit-forming substances. When used in internal combustion engines (ICE), deposits from these substances can form on and around constricted areas of the engine which come in contact with the fuel. In these ICE, such as automobile engines, deposits can build on engine intake valves leading to progressive restriction of the gaseous fuel mixture flow into the combustion chamber, in turn reducing the maximum power of the engine, decreasing fuel economy, increasing engine emissions, and hindering engine startability.
- ICE internal combustion engines
- fuel detergent additives include additives that can be described as ashless dispersants. These additives consist of hydrocarbyl backbones, including polyisobutylene (PIB) backbones, that have been combined with polar, nitrogen-containing head groups.
- PIB polyisobutylene
- the primary fuel detergent additives used today include PIB amines, PIB succinimides and PIB phenol Mannich amines.
- nitrogen-containing additives can lead to undesirable effects, such as seal degradation, particularly in the case of elastomer containing seals. Nitrogen-free additives would be free of these potential disadvantages.
- an effective fuel additive that may be used in fuel additive compositions and fuel compositions and in the operation of internal combustion engines that is free of nitrogen. There is need for such nitrogen-free additives that provide comparable and/or improved performance compared to the nitrogen-containing additives commonly used today.
- a new class of fuel detergents have been discovered which offer improvements over traditional fuel detergents such as polyisobutylene (PIB) phenol Mannich detergents.
- This new class of detergents does not contain any nitrogen, traditionally believed to be essential to the good performance of fuel detergent additives while still delivering comparable and/or improved performance compared to the nitrogen-containing additives commonly used today.
- the present invention provides a composition comprising a nitrogen- free detergent fuel additive represented by Formula I;
- R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms
- R 2 is independently a hydrocarbyl group containing 1 to 10 carbon atoms
- n is 0 or 1
- R 3 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms
- R 4 is a hydrocarbyl group containing 1 to 150 carbon atoms
- each R 5 is independently hydrogen or a hydroxyl group
- R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -OR 8 wherein R 7 is a hydrocarbyl group containing 1 to 10 carbon atoms, R 8 is hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms and m is 0 or 1; and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are free of nitrogen.
- additives of the present invention are represented by Formula II:
- R 1 is hydrogen or a hydrocarbyl group containing 1 to 6 carbon atoms
- R 2 is a hydrocarbyl group containing 1 to 6 carbon atoms
- R 3 is hydrogen or a hydrocarbyl group containing 1 to 6 carbon atoms
- R 4 is a polyisobutylene group having a number average molecular weight of 350 to 5000
- R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -OR 8 wherein R 7 is a hydrocarbyl group containing 1 to 10 carbon atoms, R 8 is hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms and m is 0 or 1.
- R 6 in Formula I and/or Formula II is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms [0010]
- the various definitions of each of the R groups listed above for Formula II may also be applied to Formula I shown above.
- the additive of the present invention comprises a mixture of one or more additives from the following list: a) the additive represented by Formula II wherein R 3 is hydrogen and R 6 is hydrogen; b) the additive represented by Formula II wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms and R 6 is hydrogen; c) the additive represented by Formula II wherein R 3 is hydrogen and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms; d) the additive represented by Formula II wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon atoms and R 6 is a hydrocarbyl group containing 1 to 6 carbon atoms [0012] In other embodiments the additive of the present invention comprises a mixture of one or more additives from the following list: a) the additive represented by Formula I wherein R 3 is hydrogen, each R 5 is hydrogen and R 6 is hydrogen; b) the additive represented by Formula I wherein R 3 is a hydrocarbyl group containing 1 to 6 carbon
- the additives of the present invention are represented by either Formula I and/or Formula II above wherein R 1 is hydrogen; R 2 is independently a methylene group, an ethylene group, a propylene group or a butylene group; R 3 is independently hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; R 5 is hydrogen; R 6 is independently hydrogen, a methyl group, an ethyl group, a propyl group or a butyl group; or combinations thereof.
- R 2 is a methylene group
- R 3 is a methyl group
- R 6 is a hydrogen group, hydroxy group or a methyl group.
- the present invention also provides for a fuel additive composition and/or concentrate comprising: one or more of the nitrogen-free detergent additives described herein; an optional solvent; and one or more optional additional performance additives.
- the present invention also provides for a fuel composition comprising: one or more of the nitrogen-free detergent additives described herein; a fuel; and one or more optional additional performance additives.
- the present invention also provides for a method of operating an internal combustion engine, comprising supplying to said engine a fuel composition comprising one or more of the nitrogen-free detergent additives described herein; a fuel; and one or more optional additional performance additives.
- the present invention also provides for a process for making the nitrogen-free detergent fuel additives of the present invention comprising reacting a hydrocarbyl-substituted hydroxy aromatic compound and an aldehyde wherein the reaction is optionally carried out in the presence of a catalyst.
- the present invention involves a fuel additive, a fuel additive composition, a fuel composition and a method for fueling an internal combustion engine, where the fuel additive is free of nitrogen.
- the fuel additive composition of the invention shows comparable and/or improved engine deposit control, allowing for improved engine performance, including but not limited to reductions in deposit-caused engine power losses, reduction in deposit-caused fuel economy losses and decreases in deposit-caused engine emissions.
- the fuel detergent additive may also be used as a corrosion inhibitor or a lubricity aid.
- the Nitrogen Free Additive [0021] The nitrogen-free fuel detergent additives of the present invention have been shown to effectively control the formation of engine deposits, including intake valve deposits.
- a nitrogen-containing polar group is required for a fuel additive to provide effective deposit control in an engine. While not wishing to be bound by theory, the polar nitrogen-containing group is believed to be necessary for good performance as the polar head may effectively associate with dirt and/or deposit particles in an engine, allowing them to be dispersed by the fuel additive and facilitate for their removal from, and/or prevent their initial deposit on, engine surfaces. With no polar group present, it is believed the additive would be much less effective at associating with dirt and deposit particles in the engine, and so would be much less effective at controlling engine deposits.
- the present invention provides nitrogen-free fuel detergent additives that are effective at controlling engine deposits, despite the fact that they are free of nitrogen, and so free of any polar nitrogen-containing groups. [0023] While not wishing to be bound by theory, it is believed that the nitrogen-free fuel detergent additives provide effective deposit control due, at least in part, to the proximity of the ortho-polar group in the adjacent position to the phenolic (or cresol) hydroxyl group or ether, as illustrated in Formula I, and Formula II, shown above.
- the fuel detergent additive of the present invention is represented by Formula I, shown above, wherein: R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 2 is independently a hydrocarbyl group containing 1 to 10, or 1 to 6 carbon atoms; n is 0 or 1; R is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 4 is a hydrocarbyl group containing 1 to 150, 10 to 150, or 50 to 150 carbon atoms; each R 5 is independently hydrogen or a hydroxyl group; R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -OR 8 wherein R7 is a hydrocarbyl group containing 1 to 10 carbon atoms, R8 is hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms and m is 0 or 1;
- hydrocarbyl groups that make up the various groups defined above are not particularly limited.
- Suitable hydrocarbyl groups include polyolefins prepared by polymerizing olefin monomers by well known polymerization methods that are also commercially available.
- Suitable olefin monomers include monoolefins, including monoolefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, and 1-decene.
- An especially useful monoolefin source is a C 4 refinery stream having a 35 to 75 weight percent butene content and a 30 to 60 weight percent isobutene content.
- Useful olefin monomers also include diolefins such as isoprene and 1,3- butadiene. Olefin monomers can also include mixtures of two or more monoolefins, of two or more diolefins, or of one or more monoolefins and one or more diolefins.
- Useful polyolefins include polyisobutylenes having a number average molecular weight of 140 to 5000, in another instance of 400 to 2500, and in a further instance of 140 or 500 to 1500 or 1100. The polyisobutylene can have a vinylidene double bond content of 5 to 69%, in a second instance of 50 to 69%, and in a third instance of 50 to 95%.
- the polyolefin can be a homopolymer prepared from a single olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. Also possible as the hydrocarbyl substituent source are mixtures of two or more homopolymers, two or more copolymers, or one or more homopolymers and one or more copolymers.
- the hydrocarbyl-substituted phenol can be prepared by alkylating phenol with an olefin or polyolefin described above, such as a polyisobutylene or polypropylene, using well-known alkylation methods.
- the vinylidene content of the R 4 hydrocarbyl group in Formula I and/or Formula II can comprise at least about 30 mole % vinylidene groups, at least about 50 mole % vinylidene groups, or at least about 70 mole % vinylidene groups.
- Such material and methods for preparing them are described in U.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823, 5,408,018, 6,562,913, 6,683,138, 7,037,999 and U.S. Publication Nos. 20040176552A1, 20050137363 and 20060079652A1, which are expressly incorporated herein by reference.
- Such products are commercially available from BASF, under the tradename GLISSOPAL® and from Texas Petrochemicals LP, under the tradename TPC 1105TM and TPC 595TM.
- R 4 hydrocarbyl group in Formula I and/or Formula II can comprise a polyisobutylene substituent derived from a conventional PIB and a high vinylidene PIB with a number average molecular weight as described above.
- Conventional PIBs generally can contain a) 45 mole % or greater, 50 mole % or greater, 55 mole % or greater, 45 to 85 mole %, 50 to 75 mole %, or 55 to 70 mole % of trisubstituted double bond isomer, b) 5 to 45 mole %, 10 to 35 mole %, 15 to 30 mole %, or 20 to 25 mole % of tetrasubstituted double bond isomer, c) 30 mole % or less, 25 mole % or less, 1 to 30 mole %, 2 to 30 mole %, or 5 to 25 mole % of alpha- and/or beta- vinylidene double bond isomer, and can have d) a 1.1 to 4, 1.2 to 3.5, or 1.5 to 3 polydispersity defined as the ratio of weight average molecular weight to number average molecular weight.
- the conventional PIB has a vinylidene double bond isomer content as described above that comprises the alpha-vinylidene double bond isomer.
- Conventional PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition, such as a C 4 hydrocarbon stream from a petroleum catalytic cracking unit, with an active acidic polymerization catalyst such as AICI 3 .
- Conventional PIBs are available commercially under numerous trade names including Parapol® from Exxon and Lubrizol® 3104 from Lubrizol.
- High vinylidene PIBs generally can contain a) 70 mole % or greater, 80 mole % or greater, 90 mole % or greater, 70 to 99.9 mole %, 80 to 99.5 mole %, or 85 to 99 mole % of alpha- and/or beta-vinylidene double bond isomer, b) 0.1 to 15 mole %, 0.5 to 12 mole %, or 1 to 10 mole % of tetrasubstituted double bond isomer, and can have c) a 1.0 or 1.1 to 3.5, a 1.2 to 3, or a 1.3 to 2.5 polydispersity.
- the high vinylidene PIB can have an alpha- vinylidene double bond isomer content of 75 to 95 mole % or 80 to 90 mole %, and in another embodiment the high vinylidene PIB can have an alpha- vinylidene double bond isomer content of 50 to 70 mole % or 55 to 65 mole %.
- High vinylidene PIBs are prepared by polymerizing isobutylene or an isobutylene containing composition with a milder acidic polymerization catalyst such as BF 3 . High vinylidene PIBs are available commercially from several producers to include BASF and Texas Petroleum Chemicals.
- the polyisobutylene substituent derived from a conventional PIB and a high vinylidene PIB can have a) an alpha- and/or beta-vinylidene double bond isomer content of 97 mole % or less, 85 mole % or less, 75 mole % or less, less than 70 mole %, 50 to 95 or 97 mole %, 55 to 80 mole %, 60 to 75 mole %, or 55 to 69 mole %, b) a trisubstituted double bond isomer content of 4 or 5 to 40 mole %, 10 to 30 mole %, or 15 to 25 mole %, c) a tetrasubstituted double bond isomer content of 5 to 20 mole %, 6 to 18 mole %, or 7 to 15 mole %, and can have d) a polydispersity of 1.1 to 3.8, 1.2 to 3.5, or 1.3 to 2.8.
- the PIB can generally have 50 to 95 mole % of alpha- and/or beta-vinylidene double bond isomer and 4 to 40 mole % of trisubstituted double bond isomer, and in other embodiments can have 60 to 75 or 55 to 69 mole % of alpha- and/or beta-vinylidene double bond isomer and 15 to 25 mole % of trisubstituted double bond isomer.
- the PIB of the PIB alkylated hydroxy aromatic compound is derived from a conventional PIB and high vinylidene PIB where the weight ratio of conventional PIB to high vinylidene PIB is respectively 0.1 :99.9 to 99.9:0.1 , 15 :85 to 60:40, or 25 :75 to 40:60.
- R 4 may be described as a polyisobutylene group with a molecular weight of 350 to 5000, 500 to 2500 or 750 to 1200.
- the groups R 1 , R 2 , R 3 and R 6 are each independently either hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
- the fuel detergent additive is represented by Formula II, shown above, wherein: R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 2 is independently a hydrocarbyl group containing 1 to 10, or 1 to 6 carbon atoms; n is 0 or 1; R is independently hydrogen or a hydrocarbyl group containing 1 to 50, 1 to 25, 1 to 10, or 1 to 6 carbon atoms; R 4 is a hydrocarbyl group containing 1 to 150, 10 to 150, or 50 to 150 carbon atoms; R 6 is independently hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms or -(R 7 ) m -OR 8 wherein R7 is a divalent hydrocarbon group containing 1 to 10 carbon atoms, R8 is hydrogen or a hydrocarbyl group containing 1 to 50 carbon atoms and m is 0 or 1; and wherein R 1 , R 2 , R 3
- the present invention is represented by Formula II wherein: R 1 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; R 2 is a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; R 3 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms; R 4 is a polyisobutylene group having a number average molecular weight of 350 to 5000, or 500 to 2500, 550 to 2000, or 750 to 1100; and R 6 is hydrogen or a hydrocarbyl group containing 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
- the R 2 group described above in Formula I and/or Formula II is a methylene group.
- the R 3 group is a methyl group and the R 6 group is a hydrogen or a methyl group.
- R 4 is a polyisobutylene group with a number average molecular weight of 500 to 2500.
- the fuel detergent additive is prepared by reacting a hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde, optionally in the presence of a base catalyst.
- the hydrocarbyl-substituted hydroxy aromatic compound is a hydrocarbyl phenol, a hydrocarbyl cresol, or a mixture thereof.
- the hydrocarbyl-substituted hydroxy aromatic compounds suitable for use in the present invention have at least one hydrocarbyl group attached to the ring structure.
- the compound has only one hydrocarbyl group, however in other embodiments the compound may have 2, 3 4 or five hydrocarbyl groups in addition to the hydroxy group, all attached to the ring structure.
- the hydrocarbyl group in the para position to the hydroxy group is typically the largest group while the other hydrocarbyl groups tend to be smaller, if they are present at all.
- the hydrocarbyl groups that are not in the para position contain from 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In other embodiments these hydrocarbyl groups are each independently hydrogen or methyl groups, such as the group present in cresol.
- the hydrocarbyl group located in the para position (represented by R 4 in Formula I and Formula II shown above) generally contains an average of at least 8, or 30, or 35 up to 350, or to 200, or to 100 carbon atoms. In one embodiment, the hydrocarbyl group is derived from a polyalkene.
- Suitable polyalkenes include homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 or to 6, or to 4 carbon atoms.
- the olefins may be monoolefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; or a polyolefinic monomer, such as diolefinic monomer, such 1,3-butadiene and isoprene.
- the interpolymer is a homopolymer.
- An example of a polymer is a polybutene. In one instance 50% of the polybutene is derived from isobutylene.
- the polyalkenes are prepared by conventional procedures.
- the hydrocarbyl substituent of the hydrocarbyl-substituted hydroxy aromatic compound is derived from a polyisobutylene.
- the hydrocarbyl groups are derived from polyalkenes having a number average molecular weight of least 250, 350, 500, or 750 up to 5000, or to 3000, or to 2000, or to 1500.
- the polyalkene is polyisobutylene with a molecular weight of 800 to 1200.
- the hydroxy aromatic compound from which the hydrocarbyl- substituted hydroxy aromatic compound is derived can comprise phenol, a polyhydroxy benzene such as catechol, an alkyl-substituted phenol such as ortho-cresol, an alkyl-substituted polyhydroxy benzene such as 3-methylcatechol, or mixtures thereof.
- the hydrocarbyl-substituted hydroxy aromatic compound can be prepared by well known alkylation methods generally involving alkylation of the hydroxy aromatic compound with a polyolefin in the presence of acidic catalyst.
- the acidic catalyst can include for example mineral acids such as a sulfuric acid acidified clay, Lewis acid catalysts such as a complex of boron trifluoride with diethyl ether or with phenol, and acidic ion exchange resins such as the Amberlyst® series of strongly acidic macroreticular resins available from Rohm and Haas.
- phenol is alkylated with a conventional polyisobutylene, a highly reactive polyisobutylene or a mixture of conventional and highly reactive polyisobutylenes in the presence of a solvent or diluent and a BF 3 catalyst between 0 and 5O 0 C as described in U. S. Patent No. 5,876,468.
- the aldehydes suitable for use in the present invention are hydrocarbon-based aldehydes, preferably lower aliphatic aldehydes.
- Suitable aldehydes include formaldehyde, benzaldehyde, acetaldehyde, the butyraldehydes, hydroxybutyraldehydes and heptanals, as well as aldehyde precursors which react as aldehydes under the conditions of the reaction such as paraformaldehyde, paraldehyde, and formalin.
- the aldehyde is Formaldehyde and/or its precursors and reaction synthons (e.g., paraformaldehyde, trioxane). Mixtures of aldehydes may be used to prepare the additive of the present invention.
- the catalyst is not overly limited and may include an esterification catalyst such as toluenesulfonic acid, sulfuric acid, aluminum chloride, boron trifluoride-triethylamine, methanesulfonic acid, hydrochloric acid, ammonium sulfate, phosphoric acid, sodium methoxide and the like. These conditions and variations thereof are well known in the art.
- the additive of the present invention is prepared in the presence of sodium methoxide.
- the fuel detergents of the present invention can be solids, semi- solids, or liquids (oils) depending on the particular alcohol(s) and/or amine(s) used in preparing them.
- compositions intended for use in fuels are typically fuel-soluble and/or stably dispersible in a fuel in which they are to be used.
- fuel-soluble as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all fuels. Rather, it is intended to mean that the composition is soluble in a fuel (hydrocarbon, non-hydrocarbon, mixtures, etc) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
- the nitrogen-free fuel detergent additives of this invention are useful as additives for fuels, in which they may function as detergents.
- the fuel detergents of the present invention can be present in fuel compositions at 1 to 10,000 ppm (where ppm is calculated on a weightweight basis).
- the fuel detergent is present in fuel compositions in ranges with lower limits of 1, 5, 10, 20, 50, 100, 150 and 200 ppm and upper limits of 10,000, 5,000, 2,500, 1,000, and 500 where any upper limit may be combined with any lower limit to provide a range for the fuel detergent present in the fuel compositions.
- the fuel detergent is present at 10 to 2500 ppm, and in another embodiment from 20-500 ppm.
- the fuel additive composition of the present invention comprises the nitrogen-free fuel detergent additive described herein and further comprises a solvent and/or one or more additional performance additives. These additive compositions, also known as concentrates, may be used to prepare fuel compositions by adding the additive composition to a fuel.
- the solvents suitable for use in the present invention include hydrocarbon solvents that provide for the additive composition's compatibility and/or homogeneity and to facilitate their handling and transfer and may include a fuel as described below.
- the solvent can be an aliphatic hydrocarbon, an aromatic hydrocarbon, an oxygen-containing composition, or a mixture thereof. In some embodiments the flash point of the solvent is generally about 25°C or higher.
- the hydrocarbon solvent is an aromatic naphtha having a flash point above 62°C or an aromatic naphtha having a flash point of 40 0 C or a kerosene with a 16% aromatic content having a flash point above 62°C.
- Aliphatic hydrocarbons include various naphtha and kerosene boiling point fractions that have a majority of aliphatic components.
- Aromatic hydrocarbons include benzene, toluene, xylenes and various naphtha and kerosene boiling point fractions that have a majority of aromatic components.
- Alcohols are usually aliphatic alcohols having about 2 to 10 carbon atoms and include ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, amyl alcohol, and 2 -methyl- 1-butanol.
- the oxygen containing composition can include an alcohol, a ketone, an ester of a carboxylic acid, a glycol and/or a polyglycol, or a mixture thereof.
- the solvent in an embodiment of the invention will be substantially free of to free of sulphur having a sulphur content in several instances that is below 50 ppm, 25 ppm, below 18 ppm, below 10 ppm, below 8 ppm, below 4 ppm, or below 2 ppm.
- the solvent can be present in the additive concentrate composition at 0 to 99 percent by weight, and in other instances at 3 to 80 percent by weight, or 10 to 70 percent by weight.
- the fuel addditive of the present invention and the additional performance additives taken separately or in combination can be present in the additive concentrate composition at 0.01 to 100 percent by weight, and in other instances can be present at 0.01 to 95 percent by weight, at 0.01 to 90 percent by weight, or at 0.1 to 80 percent by weight.
- the additive concentrate may comprise the fuel detergent of the present invention and be substantially free of any additional solvent.
- the additive concentrate containing the fuel detergent of the present invention is neat, in that it does not contain any additional solvent added to improve the material handling characteristics of the concentrate, such as its viscosity.
- the additive concentrate containing the additive of the present invention does contain some solvent.
- the additive concentrate composition, or a fuel composition containing the fuel detergent of the present invention may be prepared by admixing or mixing the components of the composition at ambient to elevated temperatures usually up to 6O 0 C until the composition is homogeneous.
- the fuel additive composition is substantially nitrogen free or nitrogen free.
- the fuel additive composition comprises the nitrogen free fuel additive described above but also comprises additional additive which may not be nitrogen free.
- the fuel composition of the present invention comprises the fuel detergent described above and a liquid fuel, and is useful in fueling an internal combustion engine.
- a fuel may also be a component of the additive compositions described above.
- Fuels suitable for use in the present invention are not overly limited. Generally, suitable fuels are normally liquid at ambient conditions e.g., room temperature (20 to 30 0 C).
- the liquid fuel can be a hydrocarbon fuel, a non- hydrocarbon fuel, or a mixture thereof.
- the hydrocarbon fuel can be a petroleum distillate, including a gasoline as defined by ASTM specification D4814, or a diesel fuel, as defined by ASTM specification D975.
- the liquid fuel is a gasoline, and in another embodiment the liquid fuel is a non-leaded gasoline.
- the liquid fuel is a diesel fuel.
- the hydrocarbon fuel can be a hydrocarbon prepared by a gas to liquid process to include for example hydrocarbons prepared by a process such as the Fischer-Tropsch process.
- the non-hydrocarbon fuel can be an oxygen containing composition, often referred to as an oxygenate, which includes an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or a mixture thereof.
- the non- hydrocarbon fuel can include for example methanol, ethanol, butanol, methyl t- butyl ether, methyl ethyl ketone, transesterified oils and/or fats from plants and animals such as rapeseed methyl ester and soybean methyl ester, and nitromethane.
- Mixtures of hydrocarbon and non-hydrocarbon fuels can include, for example, gasoline and methanol and/or ethanol, diesel fuel and ethanol, and diesel fuel and a transesterified plant oil such as rapeseed methyl ester and other bio-derived fuels.
- the liquid fuel is an emulsion of water in a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture thereof.
- the liquid fuel can have a sulphur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less.
- the fuel composition is substantially nitrogen free or nitrogen free.
- the fuel composition comprises the nitrogen free fuel additive described above but also comprises additional additive which may not be nitrogen free.
- the liquid fuel of the invention is present in a fuel composition in a major amount that is generally greater than 95% by weight, and in other embodiments is present at greater than 97% by weight, greater than 99.5% by weight, or greater than 99.9% by weight. Additional Performance Additives
- the additive compositions and fuel compositions of the present invention can further comprise one or more additional performance additives.
- Additional performance additives can be added to a fuel composition depending on several factors to include the type of internal combustion engine and the type of fuel being used in that engine, the quality of the fuel, and the service conditions under which the engine is being operated.
- the additional performance additives added are free of nitrogen.
- the additional performance additives may contain nitrogen.
- the additional performance additives can include: an antioxidant such as a hindered phenol or derivative thereof and/or a diarylamine or derivative thereof; a corrosion inhibitor such as an alkenylsuccinic acid; and/or a detergent/dispersant additive, other than the fuel detergent of the present invention, such as a polyetheramine or nitrogen containing detergent, including but not limited to PIB amine dispersants, quaternary salt dispersants, and succinimide dispersants.
- an antioxidant such as a hindered phenol or derivative thereof and/or a diarylamine or derivative thereof
- a corrosion inhibitor such as an alkenylsuccinic acid
- a detergent/dispersant additive other than the fuel detergent of the present invention, such as a polyetheramine or nitrogen containing detergent, including but not limited to PIB amine dispersants, quaternary salt dispersants, and succinimide dispersants.
- the additional performance additives may also include: a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate; a foam inhibitor such as a silicone fluid; a demulsifier such as a polyalkoxylated alcohol; a lubricity agent such as a fatty carboxylic acid; a metal deactivator such as an aromatic triazole or derivative thereof, including but not limited to benzotriazole; and/or a valve seat recession additive such as an alkali metal sulfo succinate salt.
- a cold flow improver such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate
- a foam inhibitor such as a silicone fluid
- a demulsifier such as a polyalkoxylated alcohol
- a lubricity agent such as a fatty carboxylic acid
- the additional additives may also include a biocide; an antistatic agent, a deicer, a fluidizer such as a mineral oil and/or a poly(alpha-olefin) and/or a polyether, and a combustion improver such as an octane or cetane improver.
- the additional performance additives which may be present in the fuel additive compositions and fuel compositions of the present invention also include di-ester, di-amide, ester-amide, and ester-imide friction modifiers prepared by reacting a dicarboxylic acid (such as tartaric acid) and/or a tricarboxyli acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst.
- a dicarboxylic acid such as tartaric acid
- a tricarboxyli acid such as citric acid
- These friction modifiers often derived from tartaric acid, citric acid, or derivates thereof, may be derived from amines and/or alcohols that are branched so that the friction modifier itself has significant amounts of branched hydrocarbyl groups present within it structure.
- the additional performance additives can each be added directly to the additive and/or the fuel compositions of the present invention, but they are generally mixed with the nitrogen-free fuel detergent additive to form an additive composition, or concentrate, which is then mixed with fuel to result in a fuel composition.
- the additive concentrate compositions are described in more detail above.
- the invention is useful for a liquid fuel and/or for an internal combustion engine, including either compression ignition engines or spark ignited engines.
- the internal combustion engine includes 2-stroke or 4-stroke engines fuelled with gasoline, diesel, a natural gas, a mixed gasoline/alcohol or any of the fuels described in the sections above.
- the compression ignition engines include both light duty and heavy duty diesel engines.
- the spark ignited engines include direct injection gasoline engines.
- the invention is useful in additive compositions in that the fuel detergent described above provides improved engine deposit control, allowing for improved engine performance, including but not limited to reductions in deposit-caused engine power losses, reduction in deposit-caused fuel economy losses and decreases in deposit-caused engine emissions.
- the additive compositions of the present invention may be used in a lubricating composition such that the additives are present in the lubricating system of the engine.
- the additives may also enter the combustion chamber of the engine during operation of the engine by the transfer of small amounts of the additive containing lubricating composition to the combustion chamber due to a phenomenon referred to as "blow by" where the lubricating composition, and in this case the additive composition, pass around the piston heads inside the cylinder, moving from the lubricating system of the engine into the combustion chamber.
- nitrogen free is used in its ordinary sense and means that the fuel detergent additive of the present invention contains no nitrogen atoms.
- the invention is not limited to nitrogen-free compositions, as other nitrogen-containing substances may be added to compositions that include the nitrogen-free fuel detergent described herein.
- the nitrogen content of the additive compositions and/or the fuel compositions of the present invention are less than 100 ppm, less than 50 ppm, less than 35 ppm or less than 10 ppm (where ppm is calculated on a weight: weight basis).
- the additive and/or fuel compositions of the present invention are free of nitrogen.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
- hydrocarbyl groups include: hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); hetero substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention,
- Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
- substituents as pyridyl, furyl, thienyl and imidazolyl.
- no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non- hydrocarbon substituents in the hydrocarbyl group.
- a commercially available nitrogen-containing additive is prepared by reacting 100 pbw mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) with with 8 pbw of an aldehyde and 11 pbw of a poly alky lamine in a reaction vessel which also contains a viscosity-controlling amount of organic solvent. The reaction is carried out below 85 0 C and aqueous distillate was removed from the system. The reaction product is a nitrogen-containing additive. Comparative Example 2
- PiB phenol derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and phenol, is well known in the art. It is used herein as a comparative example in the testing below. This material, as the results below show, does not perform well as a fuel additive. This poor performance is expected given the lack of nitrogen, or more specifically, the lack of a polar nitrogen group, in the additive. This same result would be expected for the additives of the present invention as they too lack a polar nitrogen group.
- Example 1 Example 1
- a nitrogen-free fuel additive is prepared by mixing 1000 grams of mid vinylidene 1000 Mn Polyisobutylene (TPC 1 105TM available from the Texas Petrochemicals LP) with 217 grams of toluene. The mixture is then charged to a reaction vessel. To the reaction vessel 281.2 grams of ortho cresol and 122 grams of toluene are charged, and the system is stirred for 15 minutes under a nitrogen blanket. Over 3 hours, 19.9 grams of boron-trifluoride etherate is added to the reaction vessel in a dropwise manner while the mixture in the reaction vessel is stirred and kept below 25°C. After the addition is complete, the mixture in the reaction vessel is stirred for 3 hours at ambient temperature.
- TPC 1 105TM available from the Texas Petrochemicals LP
- Example 2 A nitrogen-free fuel additive is prepared by mixing 165 grams of PiB cresol, derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and toluene (as described in the first part of Example 1 above), and 47.8 grams of methanol and 6.8 grams of paraformaldehyde in a reaction vessel. The reaction mixture is then stirred and heated to 55°C under a nitrogen blanket. Then 32.4 grams of a mixture of sodium methoxide at 25% actives in methanol is added to the reaction vessel subsurface over 70 minutes. After the charge is complete, the reaction mixture is heated to 60 0 C and then held at temperature for 150 minutes.
- TPC 1105TM available from the Texas Petrochemicals LP
- Example 3 The reaction mixture is then cooled back to ambient temperature and then transferred to a rotary evaporator. The material is vacuum stripped at 0.7 bar and 105 0 C to remove the methanol. The product is then cooled and collected. The collected material contains a nitrogen free additive.
- Example 3 The reaction mixture is then cooled back to ambient temperature and then transferred to a rotary evaporator. The material is vacuum stripped at 0.7 bar and 105 0 C to remove the methanol. The product is then cooled and collected. The collected material contains a nitrogen free additive.
- a nitrogen-free fuel additive is prepared by mixing 250 grams of PiB cresol, derived from mid vinylidene 1000 Mn Polyisobutylene (TPC 1105TM available from the Texas Petrochemicals LP) and toluene (as described in the first part of Example 1 above), and 73.0 grams of methanol and 10.2 grams of paraformaldehyde in a reaction vessel. The reaction mixture is then stirred and heated to 55°C under a nitrogen blanket. Then 49.7 grams of a mictuxe of sodium methoxide at 25% actives in methanol is added to the reaction vessel subsurface over 70 minutes. After the charge is complete, the reaction mixture is heated to 60 0 C and then held at temperature for 150 minutes.
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- General Chemical & Material Sciences (AREA)
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Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10807208P | 2008-10-24 | 2008-10-24 | |
PCT/US2009/061767 WO2010048469A1 (fr) | 2008-10-24 | 2009-10-23 | Additifs anticalaminants sans azote pour carburant |
Publications (2)
Publication Number | Publication Date |
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EP2361295A1 true EP2361295A1 (fr) | 2011-08-31 |
EP2361295B1 EP2361295B1 (fr) | 2017-03-15 |
Family
ID=41651417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP09744556.3A Not-in-force EP2361295B1 (fr) | 2008-10-24 | 2009-10-23 | Additifs anticalaminants sans azote pour carburant |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP2361295B1 (fr) |
CN (1) | CN102264875B (fr) |
AU (1) | AU2009308315A1 (fr) |
BR (1) | BRPI0919787A2 (fr) |
PL (1) | PL2361295T3 (fr) |
WO (1) | WO2010048469A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2784747A1 (fr) * | 2009-12-17 | 2011-07-14 | The Lubrizol Corporation | Additifs sans azote de controle de depot pour carburant et procede en une etape pour leur fabrication |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3306938A (en) * | 1963-10-08 | 1967-02-28 | Gen Aniline & Film Corp | Dialkylol alkylphenol process |
US4273891A (en) * | 1974-03-15 | 1981-06-16 | The Lubrizol Corporation | Hydrocarbon-substituted methylol phenols |
US5399277A (en) * | 1993-10-08 | 1995-03-21 | Exxon Chemical Patents Inc. | Fuel and lubricant additives derived from dihydroxyaromatic compounds |
CN1232864A (zh) * | 1998-04-23 | 1999-10-27 | 李宝清 | 发动机燃料系统免拆清洗剂 |
JP2000229900A (ja) * | 1999-02-09 | 2000-08-22 | Mitsubishi Materials Corp | 水酸基を有する芳香族化合物の製造方法 |
CN1166752C (zh) * | 2001-03-20 | 2004-09-15 | 中油燃料油股份有限公司 | 一种高硫重质燃料油脱硫剂及其应用 |
US7402186B2 (en) * | 2004-02-09 | 2008-07-22 | The Lubrizol Corporation | Fuel composition containing a medium substantially free of sulphur and process thereof |
-
2009
- 2009-10-23 BR BRPI0919787A patent/BRPI0919787A2/pt not_active IP Right Cessation
- 2009-10-23 WO PCT/US2009/061767 patent/WO2010048469A1/fr active Application Filing
- 2009-10-23 CN CN200980152043.9A patent/CN102264875B/zh not_active Expired - Fee Related
- 2009-10-23 AU AU2009308315A patent/AU2009308315A1/en not_active Abandoned
- 2009-10-23 PL PL09744556T patent/PL2361295T3/pl unknown
- 2009-10-23 EP EP09744556.3A patent/EP2361295B1/fr not_active Not-in-force
Non-Patent Citations (1)
Title |
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See references of WO2010048469A1 * |
Also Published As
Publication number | Publication date |
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BRPI0919787A2 (pt) | 2018-05-29 |
WO2010048469A1 (fr) | 2010-04-29 |
PL2361295T3 (pl) | 2017-09-29 |
AU2009308315A1 (en) | 2010-04-29 |
EP2361295B1 (fr) | 2017-03-15 |
CN102264875B (zh) | 2014-01-22 |
CN102264875A (zh) | 2011-11-30 |
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