WO2024083782A1 - Fuel compositions - Google Patents
Fuel compositions Download PDFInfo
- Publication number
- WO2024083782A1 WO2024083782A1 PCT/EP2023/078759 EP2023078759W WO2024083782A1 WO 2024083782 A1 WO2024083782 A1 WO 2024083782A1 EP 2023078759 W EP2023078759 W EP 2023078759W WO 2024083782 A1 WO2024083782 A1 WO 2024083782A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polybutene
- fuel composition
- polymer
- gasoline
- group
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 162
- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 239000003502 gasoline Substances 0.000 claims abstract description 106
- 229920001083 polybutene Polymers 0.000 claims abstract description 93
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 238000002485 combustion reaction Methods 0.000 claims abstract description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 29
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 9
- 229920002367 Polyisobutene Polymers 0.000 claims description 48
- 230000009257 reactivity Effects 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 25
- -1 anthracyl Chemical group 0.000 claims description 15
- 230000001965 increasing effect Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 description 48
- 229930195733 hydrocarbon Natural products 0.000 description 31
- 150000002430 hydrocarbons Chemical class 0.000 description 27
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 24
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 230000000996 additive effect Effects 0.000 description 19
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003599 detergent Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920002368 Glissopal ® Polymers 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002816 fuel additive Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 150000005199 trimethylbenzenes Chemical class 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006683 Mannich reaction Methods 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-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
- UZVAZDQMPUOHKP-UHFFFAOYSA-N 2-(7-methyloctyl)phenol Chemical compound CC(C)CCCCCCC1=CC=CC=C1O UZVAZDQMPUOHKP-UHFFFAOYSA-N 0.000 description 1
- TZGPACAKMCUCKX-UHFFFAOYSA-N 2-hydroxyacetamide Chemical class NC(=O)CO TZGPACAKMCUCKX-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N trimethylbenzene Natural products CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0415—Light distillates, e.g. LPG, naphtha
- C10L2200/0423—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
Definitions
- the present invention relates to a liquid fuel composition, in particular to a liquid fuel composition which provides improved engine power and which has a reduced burn duration in an internal combustion engine.
- the present invention also relates to methods of improving the power output of an internal combustion engine as well as increasing efficiency and reducing emissions, by fueling the internal combustion engine with the liquid fuel composition described herein below.
- the present invention also relates to methods of reducing the burn duration of a liquid fuel composition.
- gasoline fuel compositions containing specially formulated refinery components with high octane and flame speed/burn duration properties can deliver increases in power and/or acceleration as well as fuel economy.
- it would be desirable to be able to use market available, standard exchange gasoline fuel for upgrading power, acceleration and fuel efficiency performance So-called high reactivity polybutene polymers have relatively high proportions (i.e. >30%) of polymer molecules having a terminal vinylidene group.
- US 6,048,373 discloses a fuel composition comprising a spark ignition fuel, a Mannich detergent and a polybutene having a molecular weight distribution of less than 1.4 for controlling intake valve deposits and minimizing valve sticking in spark ignition internal combustion engines.
- Preferred polybutenes disclosed therein have a number average molecular weight (Mn) of from about 500 to about 2000, and high reactivity polyisobutylenes (PIBs) are disclosed.
- Preferred treat rates for the polybutene(s) having a molecular weight distribution of 1.4 or less are stated to fall within the range of about 0.5 to about 50 ptb, preferably in the range of about 1.5 to about 40 ptb.
- the treat rate of the high reactivity PIB used in Example 2 is 53.2 ptb which is equivalent to about 151 ppm.
- a low molecular weight polybutene polymer at selected treat rates for providing increased engine power and reduced burn duration.
- Co-pending US patent application 63/390715 discloses a fuel composition comprising a gasoline base fuel and a high-reactivity polybutene polymer for providing improved engine power.
- Co-pending US patent application 63/179767 discloses a fuel composition comprising a base fuel and a tetraalkylethane compound such as dicumene for providing improved engine power.
- a low molecular weight polybutene such as a low molecular weight polyisobutylene (PIB), especially a low molecular weight, high reactivity, polyisobutylene (PIB) in combination with a selected tetraalkylethane compound in a gasoline fuel composition, preferably at selected additive treat rates, can provide synergistic benefits in terms of improved power output (increased P max ) and reduced burn duration, even when a standard exchange gasoline fuel is used.
- a reduction in burn duration leads to a more complete burn per cycle, which improves engine efficiency as well as lowers harmful emissions including particulate matter (PM/PN).
- a fuel composition comprising:
- polybutene polymer (b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group;
- the fuel compositions of the present invention provide improved power output as reflected in increased P max , as well as reduced burn duration of the fuel. Further the fuel compositions of the present invention exhibit excellent acceleration, energy efficiency and fuel economy.
- liquid fuel composition for improving power output of an internal combustion engine, wherein the liquid fuel composition comprises:
- polybutene polymer (b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein the polybutene is a high reactivity polybutene wherein greater than 30% of the polymer molecules in the polyisobutylene polymer have a terminal vinylidene group; and
- each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH 2 )nOH or (CH 2 ) n NH 2 , wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX 2 group is a hydrogen atom.
- a method of increasing the power output of a spark ignition internal combustion engine comprising adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and wherein the tetraalkylethane compound has the formula
- each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH 2 ) n OH or (CH 2 ) n NH 2 , wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX 2 group is a hydrogen atom, and combusting the fuel composition in the spark ignition internal combustion engine.
- a method of reducing the burn duration of a liquid fuel composition in an internal combustion engine comprising adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and wherein the tetraalkylethane compound has the formula (I): wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH 2 ) n OH or (CH 2 ) n NH 2 , wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen
- Figure 1 is a graphical representation of the P max measurements for Example 1 and its reference base fuel.
- Figure 2 is a graphical representation of the Pmax measurements for Examples 2-4 and their reference base fuel.
- Figure 3 is a graphical representation of the Pmax measurements for Examples 5-13 and their reference base fuel.
- Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel.
- Figure 6 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 14-27) and the base fuel control at 1300 rpm, 15 IMEP, IGN at TDC.
- power output refers to the amount of resistance power required to maintain a fixed speed at wide open throttle conditions in Chassis Dynamometer testing.
- 'P max ' refers to the direct measurement of the force generated by decomposition of the fuel.
- the term "improving" embraces any degree of improvement.
- the improvement may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more, even more especially 5% or more, of the power output or Pmax provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
- the improvement in power output or Pmax may even be as high as 10% of the power output or P ma x provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
- a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound may also be used to improve the acceleration of an internal combustion engine.
- acceleration refers to the amount of time required for the engine to increase in speed between two fixed speed conditions in a given gear.
- the term “improving” embraces any degree of improvement, and may be improved by the same percentages as the power and or Pmax is increased above.
- the power output and acceleration provided by a fuel composition may be determined in any known manner for instance using the standard test methods as set out in SAE Paper 2005- 01-0239 and SAE Paper 2005-01-0244.
- 'burn duration' as used herein means the time required (in engine crank angle degrees) for combustion to progress from 10% to 90% (referred to as Al 10-90 in the Examples below).
- Al 50-90 is also used in relation to burn duration and means the time required (in engine crank angle degrees) for combustion to progress from 50% to 90%.
- a method of reducing the burn duration of a gasoline fuel composition comprising adding a polybutene polymer and a tetraalkylethane compound to the gasoline fuel composition, wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol and wherein the tetraalkylethane compound has the formula (I):
- the burn duration of a fuel composition may be determined in any known manner, for instance using the test method disclosed in the Examples section hereinbelow.
- the term "reducing the burn duration" embraces any degree of reduction.
- the reduction may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more and even more especially 4% or more, or 5% or more reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
- the reduction in burn duration may even be as high as a 10% reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
- LES laminar flame speed'
- LFS Laminar Burning Velocity
- the following method for measuring flame speed uses a net pressure method: Mittal, M., Zhu, G. and Schock H., 'Fast mass-fraction-burned calculation using the net pressure method for real-time applications', Proc. Instn Meeh Engrs, Part D: J. Automobile Engineering 223 (3) (2009): 389-394.
- the liquid fuel composition of the present invention comprises a base fuel suitable for use in an internal combustion engine, a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound.
- the base fuel suitable for use in an internal combustion engine is a gasoline or a diesel fuel, and therefore the liquid fuel composition of the present invention is typically a gasoline composition or a diesel fuel composition.
- the base fuel is a gasoline base fuel.
- the polybutene for use herein is preferably a high reactivity polybutene.
- a high reactivity polybutene is a polybutene having a relatively high proportion, i.e. greater than 30%, of polymer molecules having a terminal vinylidene group.
- the term 'polybutene' as used herein includes polymers made from pure or substantially pure 1- butene or isobutene, and polymers made from mixtures of two or all three of 1-butene, 2-butene and isobutene, as well as including polymers containing minor amounts, preferably less than 10% by weight, more preferably less than 5% by weight, of C2, C3, and C5 and higher olefins as well as diolefins.
- the polybutene is a polyisobutene (also referred to as 'polyisobutylene') preferably wherein at least 90% by weight, more preferably at least 95% by weight, of the polymer is derived from isobutene.
- the polybutene is a high reactivity polyisobutylene.
- the high reactivity polybutene has greater than 40% of polymer molecules having a terminal vinylidene group.
- the high reactivity polybutene polymer has greater than 50% of polymer molecules having a terminal vinylidene group.
- the high reactivity polybutene has more than 85% of its double bonds located in the terminal position of the molecule.
- the high reactivity polybutene polymer for use herein preferably has a molecular mass distribution of 1.5 or greater, preferably 1.6 or greater, more preferably 1.7 or greater, even more preferably 1.8 or greater.
- the polybutene polymer is present at a level of from 500ppm to 5000ppm. In one embodiment, the polybutene polymer is present at a level of from 1000 ppm to 5000 ppm. In another embodiment the polybutene polymer is present at a level of from 2500 to 5000 ppm, by weight of the fuel composition. Examples of preferred levels of polybutene include lOOOppm, 2500ppm and 5000ppm, by weight of the fuel composition.
- One or more polybutene polymer can be used in the fuel compositions herein. When more than one polybutene polymer is used herein, the total level of polybutene polymer is the same as the ranges given in the previous paragraph.
- the polybutene polymer for use herein is a low molecular weight polybutene polymer.
- the term 'low molecular weight polybutene' means a polybutene polymer having a number average molecular weight (M n ) in the range from 200 to 10,000 g/mol, preferably from 500 to 5000 g/mol, more preferably from 1000 to 5000 g/mol.
- the polybutenes, preferably high reactivity polybutenes, for use herein have a number average molecular weight (M n ) from 1000 to 2300 g.mol.
- the polybutenes for use herein have a number average molecular weight (M n ) from 2300 to 5000 g/mol.
- M n number average molecular weight
- the number average molecular weight of the polybutene polymer can be determined using Gel Permeation Chromatography.
- the high reactivity polybutenes for use herein may be bioderived or non-bioderived.
- the polybutene is a low molecular weight, high reactivity polyisobutylene which is derived from
- the high reactivity polybutenes for use herein preferably contain less than 1 mg/kg of chlorine.
- the high reactivity polybutene polymer for use herein has a kinematic viscosity at 100°C of 190 mm 2 /s or greater, preferably in the range of 190 mm 2 /s to 1500 mm 2 /s, more preferably in the range from 430 to 1500 mm 2 /s.
- a preferred high reactivity polybutene for use herein has an alpha olefin content of greater than 85%.
- Suitable high reactivity polybutenes for use herein include those commercially available from BASF under the tradename Glissopal (RTM) such as Glissopal (RTM) 1000, Glissopal (RTM) 1300 and Glissopal (RTM) 2300.
- Glissopal RTM
- RTM Glissopal
- Glissopal (RTM) 1000 has a number average molecular weight (M n ) of 1000 g/mol, a molecular mass distribution (M w /M n ) of 1.6, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm 2 /s and a chlorine content of less than 1 mg/kg.
- Glissopal (RTM) 1300 has a number average molecular weight (M n ) of 1300 g/mol, a molecular mass distribution (M w /M n ) of 1.7, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm 2 /s and a chlorine content of less than 1 mg/kg.
- Glissopal (RTM) 2300 has a number average molecular weight (M n ) of 2300, a molecular mass distribution (M w /M n ) of 1.6, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm 2 /s and a chlorine content of less than 1 mg/kg.
- Glissopal 1000, 1300 and 2300 BMBcert (TM) which are low molecular weight, highly reactive polyisobutenes derived from 100% renewable feedstock, commercially available from BASF.
- the polybutene polymer may be blended together with any other additives in addition to the tetraalkylethane compound e.g. additive performance package(s) to produce an additive blend.
- the additive blend is then added to a base fuel to produce a liquid fuel composition.
- the tetraalkylethane compound used herein is a compound having the formula (I): wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 saturated or unsaturated alkyl group, (CH2)nOH, (CH2)nNH2, wherein n is in the range from 1 to 9, preferably in the range from 1 to 6, more preferably in the range from 1 to 4, even more preferably in the range from 1 to 3, provided that at least one of the X groups in each CX3 group is a hydrogen atom.
- Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 saturated or unsaturated alkyl group, (CH2)nOH, (CH2)nNH2, wherein n is in the range from 1 to 9, preferably in the range from 1 to 6, more preferably in the range from 1 to 4, even
- each CX3 group is a hydrogen atom.
- three of the X groups in each CX3 group is a hydrogen atom.
- the Ar of the tetraalkylethane compound is a substituted or unsubstituted aromatic group, such as a phenyl, biphenyl, naphthyl, thienyl or anthracyl. More preferably, Ar is an unsubstituted phenyl group.
- cumene which is commercially available.
- dicumene can be prepared by several known methods, as described in US4,072,811.
- each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated or unsaturated C1-C6, more preferably C 1 -C 3 , alkyl group, provided that at least one of the X groups in each CX3 group is a hydrogen atom. More preferably, each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated C1-C6, preferably C1-C3, alkyl group, provided that at least one of the X groups in each CX 3 group is a hydrogen atom.
- each X group is independently selected from a hydrogen atom, and an unsubstituted straight chain, saturated C1-C6, preferably C1-C3, alkyl group, especially methyl, ethyl and propyl.
- suitable tetraalkylethane compounds of Formula (I) include:
- the tetralkylethane compound is 1,1'(1,1,2,2-tetramethyl-l,1-ethanediyl)bis- benzene Dicumene is commercially available from Aldrich and various other chemical suppliers.
- the tetraalkylethane compound is preferably present in the fuel composition at a level from 30ppm to 10 wt%, preferably from 100ppm to 5 wt%, more preferably from 100ppm to 1 wt%, even more preferably from 100ppm to 5000ppm. In one embodiment, the tetraalkylethane is present at a level from 313ppm to 5000ppm, by weight of the fuel composition.
- the tetraalkylethane compound may be blended together with any other additives in addition to the polybutene polymer e.g. additive performance package(s) to produce an additive blend.
- the additive blend is then added to a base fuel to produce a liquid fuel composition.
- the amount of performance package(s) in the additive blend is preferably in the range of from 0.1 to 99.8 wt%, more preferably in the range of from 5 to 50 wt%, by weight of the additive blend.
- the amount of the performance package present in the liquid fuel composition of the present invention is in the range of 15 ppmw (parts per million by weight) to 10 %wt, based on the overall weight of the liquid fuel composition.
- the amount of the performance package present in the liquid fuel composition of the present invention additionally accords with one or more of the parameters (i) to (xv) listed below: (i) at least 100 ppmw (ii) at least 200 ppmw (iii) at least 300 ppmw (iv) at least 400 ppmw (v) at least 500 ppmw (vi) at least 600 ppmw (vii) at least 700 ppmw (viii) at least 800 ppmw (ix) at least 900 ppmw (x) at least 1000 ppmw (xi) at least 2500ppmw (xii) at most 5000ppmw (xiii) at most 10000 ppmw (xiv) at most 2 %wt.
- a further preferred additive for use in the fuel compositions herein, in combination with the tetralkylethane compound and the polybutene polymer is an alkylbenzene compound having the f n each R1-R6 gr R1 R2ormula (II) wherei R R65 R4 R3ently selected from hydrogen and a C 1 -C 6 alkyl group, wherein at least one of the R1-R6 groups is a C1-C6 alkyl group.
- three R1-R6 groups in the alkylbenzene compound are independently selected from a C1-C6 alkyl group.
- the alkylbenzene compound is a trimethylbenzene compound.
- the alkykbenzene compound is 1,3,5-trimethylbenzene. 1,3,5-trimethylbenzene is commercially available from Aldrich and other chemical suppliers.
- the alkylbenzene compound is a mixture of trimethylbenzene isomers (known as mesitylene).
- the alkylbenzene compound is preferably present in the fuel composition at a level from 30ppm to 2 wt%, preferably from lOOppm to 1 wt%, more preferably from lOOppm to 5000ppm, even more preferably from 500ppm to 2000ppm, by weight of the fuel composition.
- the alkylbenzene compound, the tetraalkylethane compound and the polybutene polymer may be blended together with any other additives e.g. additive performance package(s) to produce an additive blend.
- the additive blend is then added to a base fuel to produce a liquid fuel composition.
- the gasoline may be any gasoline suitable for use in an internal combustion engine of the spark-ignition (petrol) type known in the art, including automotive engines as well as in other types of engine such as, for example, off road and aviation engines.
- the gasoline used as the base fuel in the liquid fuel composition of the present invention may conveniently also be referred to as 'base gasoline'.
- the gasoline may also comprise various levels of bio-components and bio-streams at any level while maintaining appropriate analytical specifications.
- the bio-components may come from any biomass conversion processes including variations of uncatalyzed and catalyzed biomass pyrolyses, hydro-thermal liquefaction, non-thermal biomass conventions such as microbe catalyzed biochemical processes, etc. Any biomass suitable as feedstock to these processes is ideal.
- Gasolines typically comprise mixtures of hydrocarbons boiling in the range from 25 to 230°C (EN- ISO 3405), the optimal ranges and distillation curves typically varying according to climate and season of the year.
- the hydrocarbons in a gasoline may be derived by any means known in the art, conveniently the hydrocarbons may be derived in any known manner from straight-run gasoline, synthetically-produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbons, hydro-cracked petroleum fractions, catalytically reformed hydrocarbons or mixtures of these.
- the specific distillation curve, hydrocarbon composition, research octane number (RON) and motor octane number (MON) of the gasoline are not critical.
- gasolines comprise components selected from one or more of the following groups; saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons.
- the gasoline may comprise a mixture of saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and, optionally, oxygenated hydrocarbons.
- the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 40 percent by volume based on the gasoline (ASTM D1319); preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 30 percent by volume based on the gasoline, more preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 20 percent by volume based on the gasoline.
- the aromatic hydrocarbon content of the gasoline is in the range of from 0 to 70 percent by volume based on the gasoline (ASTM D1319), for instance the aromatic hydrocarbon content of the gasoline is in the range of from 10 to 60 percent by volume based on the gasoline; preferably, the aromatic hydrocarbon content of the gasoline is in the range of from 0 to 50 percent by volume based on the gasoline, for instance the aromatic hydrocarbon content of the gasoline is in the range of from 10 to 50 percent by volume based on the gasoline.
- the gasoline base fuel comprises less than 10 vol% of aromatics, based on the total base fuel. In another embodiment herein, the gasoline base fuel comprises less than 2 vol% of aromatics having 9 carbon atoms or greater, based on the total base fuel.
- the benzene content of the gasoline is at most 10 percent by volume, more preferably at most 5 percent by volume, especially at most 1 percent by volume based on the gasoline.
- the gasoline preferably has a low or ultra low sulphur content, for instance at most 1000 ppmw (parts per million by weight), preferably no more than 500 ppmw, more preferably no more than 100, even more preferably no more than 50 and most preferably no more than even 10 ppmw.
- the gasoline also preferably has a low total lead content, such as at most 0.005 g/1, most preferably being lead free - having no lead compounds added thereto (i.e. unleaded).
- the oxygenate content of the gasoline may be up to 85 percent by weight (EN 1601) (e.g. ethanol per se) based on the gasoline.
- the oxygenate content of the gasoline may be up to 35 percent by weight, preferably up to 25 percent by weight, more preferably up to 10 percent by weight.
- the oxygenate concentration will have a minimum concentration selected from any one of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 percent by weight, and a maximum concentration selected from any one of 12, 8, 7.2, 5, 4.5, 4.0, 3.5, 3.0, and 2.7 percent by weight.
- oxygenated hydrocarbons examples include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen containing heterocyclic compounds.
- the oxygenated hydrocarbons that may be incorporated into the gasoline are selected from alcohols (such as methanol, ethanol, propanol, 2- propanol, butanol, tert-butanol, iso-butanol and 2- butanol), ethers (preferably ethers containing 5 or more carbon atoms per molecule, e.g., methyl tert-butyl ether and ethyl tert-butyl ether) and esters (preferably esters containing 5 or more carbon atoms per molecule); a particularly preferred oxygenated hydrocarbon is ethanol.
- oxygenated hydrocarbons When oxygenated hydrocarbons are present in the gasoline, the amount of oxygenated hydrocarbons in the gasoline may vary over a wide range.
- gasolines comprising a major proportion of oxygenated hydrocarbons are currently commercially available in countries such as Brazil and U.S.A., e.g. ethanol per se and E85, as well as gasolines comprising a minor proportion of oxygenated hydrocarbons, e.g. E10 and E5. Therefore, the gasoline may contain up to 100 percent by volume oxygenated hydrocarbons.
- E100 fuels as used in Brazil are also included herein.
- the amount of oxygenated hydrocarbons present in the gasoline is selected from one of the following amounts: up to 85 percent by volume; up to 70 percent by volume; up to 65 percent by volume; up to 30 percent by volume; up to 20 percent by volume; up to 15 percent by volume; and, up to
- the gasoline may contain at least 0.5, 1.0 or 2.0 percent by volume oxygenated hydrocarbons.
- gasolines which have an olefinic hydrocarbon content of from 0 to 20 percent by volume (ASTM D1319), an oxygen content of from 0 to 5 percent by weight (EN 1601), an aromatic hydrocarbon content of from 0 to 50 percent by volume (ASTM D1319) and a benzene content of at most 1 percent by volume.
- gasoline blending components which can be derived from sources other than crude oil, such as low carbon gasoline fuels from either biomass or CO2, and blends thereof which each other or with fossil-derived gasoline streams and components.
- sources other than crude oil such as low carbon gasoline fuels from either biomass or CO2
- blends thereof which each other or with fossil-derived gasoline streams and components.
- suitable examples of such fuels include:
- Biomass derived a. Straight run bio-naphthas from hydrodeoxygenation of biomass, and b. cracked and/or isomerized products of syn-wax (biomass gasification to syngas (CO/H2) then to syn-wax by the Fischer-Tropsch (FT) process, which is then hydrocracked/hydroisomerized to yield a slate of products including cuts in the gasoline distillation range.
- FT Fischer-Tropsch
- CO2 derived a. CO2 + H2 syngas (CO/H2) by modified water/gas shift reaction, then to syn-wax by the FT process), which is then hydrocracked/hydroisomerized to yield a slate of products including cuts in the gasoline distillation range.
- Methanol derived a. Biomass gasification to syngas (CO/H2), then to Methanol and then gasoline by the MTG process (MTG is 'methanol-to-gasoline' process).
- MTG is 'methanol-to-gasoline' process.
- H2 used in all processes would be renewable (green) H2 from electrolysis of water using renewable electricity such as from wind and solar.
- gasoline blending components which can be derived from a biological source. Examples of such gasoline blending components can be found in W02009/077606, W02010/028206, WO2010/000761, European patent application nos. 09160983.4, 09176879.6, 09180904.6, and US patent application serial no. 61/312307.
- the base gasoline or the gasoline composition of the present invention may conveniently include one or more optional fuel additives, in addition to the low molecular weight, preferably high reactivity, polybutene and the tetraalkylethane compound.
- concentration and nature of the optional fuel additive(s) that may be included in the base gasoline or the gasoline composition of the present invention is not critical.
- Non-limiting examples of suitable types of fuel additives that can be included in the base gasoline or the gasoline composition of the present invention include anti-oxidants, corrosion inhibitors, detergents, dehazers, antiknock additives, metal deactivators, valve-seat recession protectant compounds, dyes, solvents, carrier fluids, diluents and markers. Examples of suitable such additives are described generally in US Patent No. 5,855,629.
- the fuel additives can be blended with one or more solvents to form an additive concentrate, the additive concentrate can then be admixed with the base gasoline or the gasoline composition of the present invention.
- the (active matter) concentration of any optional additives present in the base gasoline or the gasoline composition of the present invention is preferably up to 1 percent by weight, more preferably in the range from 5 to 2000 ppmw, advantageously in the range of from 300 to 1500 ppmw, such as from 300 to 1000 ppmw.
- corrosion inhibitors for example based on ammonium salts of organic carboxylic acids, said salts tending to form films, or of heterocyclic aromatics for nonferrous metal corrosion protection; dehazers; anti-knock additives; metal deactivators; solvents; carrier fluids; diluents; antioxidants or stabilizers, for example based on amines such as phenyldiamines, e.g.
- p-phenylenediamine N,N'-di- sec-butyl-p-phenyldiamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxy- phenylpropionic acid; anti-static agents; metallocenes such as ferrocene; methylcyclopentadienylmanganese tricarbonyl; lubricity additives, such as certain fatty acids, alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and also dyes (markers).
- phenols such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxy- phenylpropionic acid
- anti-static agents metallocenes such as ferrocene
- anti valve seat recession additives such as sodium or potassium salts of polymeric organic acids.
- the gasoline compositions herein can also comprise a detergent additive.
- Suitable detergent additives include those disclosed in W02009/50287, incorporated herein by reference.
- Preferred detergent additives for use in the gasoline composition herein typically have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (Mn) of from 85 to 20000 and at least one polar moiety selected from:
- the hydrophobic hydrocarbon radical in the above detergent additives which ensures the adequate solubility in the base fluid, has a number-average molecular weight (Mn) of from 85 to 20000, especially from 113 to 10000, in particular from 300 to 5000.
- Typical hydrophobic hydrocarbon radicals especially in conjunction with the polar moieties (Al), (A8) and (A9), include polyalkenes (polyolefins), such as the polypropenyl, polybutenyl and polyisobutenyl radicals each having Mn of from 300 to 5000, preferably from 500 to 2500, more preferably from 700 to 2300, and especially from 700 to 1000.
- Non-limiting examples of the above groups of detergent additives include the following:
- Additives comprising mono- or polyamino groups are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn of from 300 to 5000.
- polybutene or polyisobutene having predominantly internal double bonds are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
- the amines used here for the amination may be, for example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylene- triamine, triethylenetetramine or tetraethylenepentamine.
- Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
- Further preferred additives comprising monoamino groups (A1) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization of from 5 to 100, with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946.
- additives comprising monoamino groups (A1) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.
- Additives comprising polyoxy-C 2 -C 4 -alkylene moieties are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 - alkylcyclohexanols or C 1 -C 30 -alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyether-amines, by subsequent reductive amination with ammonia, monoamines or polyamines.
- Such products are described in particular in EP-A-310 875, EP- A-356 725, EP-A-700 985 and US-A-4 877 416.
- polyethers such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.
- Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups are preferably corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by reacting conventional or highly reactive polyisobutene having Mn of from 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene.
- derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such additives are described in particular in US-A-4849572.
- Additives comprising moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
- the polyisobutenyl-substituted phenols may stem from conventional or highly reactive polyisobutene having Mn of from 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831141.
- the detergent additive used in the gasoline compositions of the present invention contains at least one nitrogen-containing detergent, more preferably at least one nitrogen-containing detergent containing a hydrophobic hydrocarbon radical having a number average molecular weight in the range of from 300 to 5000.
- the nitrogen-containing detergent is selected from a group comprising polyalkene monoamines, polyetheramines, polyalkene Mannich amines and polyalkene succinimides.
- the nitrogen- containing detergent may be a polyalkene monoamine.
- amounts (concentrations, % vol, ppmw, % wt) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
- the liquid fuel composition of the present invention can be produced by admixing the essential low molecular weight, preferably high reactivity, polybutene polymer and the essential tetraalkylethane compound with a gasoline base fuel suitable for use in an internal combustion engine. Since the base fuel to which the essential fuel additive is admixed is a gasoline, then the liquid fuel composition produced is a gasoline composition.
- the internal combustion engine herein is a spark ignition internal combustion engine operating in either PFI (Port fuel injection) or GDI (gasoline direct injection) mode.
- PFI Port fuel injection
- GDI gasoline direct injection
- Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
- Example 1 used an E10 base fuel having a RON of 92.3
- Examples 2-4 used an E10 base fuel having a RON of 96.7
- Examples 5-13 used an E10 base fuel having a RON of 96.5.
- High reactivity polyisobutylene (HR-PIB) and/or dicumene were added into the base fuel at the treat rates indicated in Tables 1 and 2 below. Some of the Examples also included mesitylene, as indicated. Mesitylene is a mixture of trimethylbenzene isomers. Tables 1 and 2 also show the RON and MON values for each fuel formulation.
- the engine used for these experiments was the Gasoline single cylinder engine in PFI mode. This engine was manufactured by AVL and based on the EA8882.OL Audi TFSI/VW TSI (Euro 6). The single cylinder bench engine details are shown in Table 3 below.
- Figure 1 is a graphical representation of the Pmax measurements for Example 1 and its reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
- Figure 2 is a graphical representation of the Pmax measurements for Examples 2-4 and their reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
- Figure 3 is a graphical representation of the Pmax measurements for Examples 5-13 and their reference base fuel (the Example number being on the x axis and P max being on the y axis).
- the Example number is on the x axis and the average % difference in burn duration and average % difference in P max is on the y axis. Examples 14-27
- Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
- the engine used for these experiments was the Gasoline single cylinder engine in GDI mode. This engine was manufactured by AVL and based on the EA8882.0L Audi
- Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel.
- the Example number is on the x axis and the Pmax is on the y axis).
- Figure 6 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 14-27) and the base fuel control at 1300 rpm, 15 IMEP, IGN at TDC.
- the Example number is on the x axis and the average % difference in burn duration and average % difference in Pmax is on the y axis.
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Abstract
Fuel composition comprising: (a) a gasoline base fuel suitable for use in a spark ignition internal combustion engine; and (b) a polybutene polymer, wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol and wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and (c) a tetraalkylethane compound having the formula (I): wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen atom. The fuel compositions of the present invention provide improved engine power and reduced burn duration.
Description
FUEL COMPOSITIONS
Field of the Invention
The present invention relates to a liquid fuel composition, in particular to a liquid fuel composition which provides improved engine power and which has a reduced burn duration in an internal combustion engine. The present invention also relates to methods of improving the power output of an internal combustion engine as well as increasing efficiency and reducing emissions, by fueling the internal combustion engine with the liquid fuel composition described herein below. The present invention also relates to methods of reducing the burn duration of a liquid fuel composition. Background of the Invention
In order to improve engine efficiency, power and acceleration properties of modern spark ignition interal combustion engines, these engines are increasingly being downsized and boosted as well as moving up in compression ratios.
As well as upgrading the engine hardware, it is also possible to improve engine efficiency, reduce emissions, increase power and acceleration of spark ignition engines by making changes to the fuel formulations used to fuel the engines. For example, gasoline fuel compositions containing specially formulated refinery components with high octane and flame speed/burn duration properties can deliver increases in power and/or acceleration as well as fuel economy. However, it would be desirable to be able to use market available, standard exchange gasoline fuel for upgrading power, acceleration and fuel efficiency performance .
So-called high reactivity polybutene polymers have relatively high proportions (i.e. >30%) of polymer molecules having a terminal vinylidene group. US 6,048,373 discloses a fuel composition comprising a spark ignition fuel, a Mannich detergent and a polybutene having a molecular weight distribution of less than 1.4 for controlling intake valve deposits and minimizing valve sticking in spark ignition internal combustion engines. Preferred polybutenes disclosed therein have a number average molecular weight (Mn) of from about 500 to about 2000, and high reactivity polyisobutylenes (PIBs) are disclosed. Preferred treat rates for the polybutene(s) having a molecular weight distribution of 1.4 or less are stated to fall within the range of about 0.5 to about 50 ptb, preferably in the range of about 1.5 to about 40 ptb. The treat rate of the high reactivity PIB used in Example 2 is 53.2 ptb which is equivalent to about 151 ppm. However, there is no teaching in this document of the use of a low molecular weight polybutene polymer at selected treat rates for providing increased engine power and reduced burn duration.
Co-pending US patent application 63/390715 discloses a fuel composition comprising a gasoline base fuel and a high-reactivity polybutene polymer for providing improved engine power.
Co-pending US patent application 63/179767 discloses a fuel composition comprising a base fuel and a tetraalkylethane compound such as dicumene for providing improved engine power.
It has now surprisingly been found that the use of a a low molecular weight polybutene, such as a low molecular weight polyisobutylene (PIB), especially a low molecular weight, high reactivity, polyisobutylene (PIB)
in combination with a selected tetraalkylethane compound in a gasoline fuel composition, preferably at selected additive treat rates, can provide synergistic benefits in terms of improved power output (increased Pmax) and reduced burn duration, even when a standard exchange gasoline fuel is used. A reduction in burn duration leads to a more complete burn per cycle, which improves engine efficiency as well as lowers harmful emissions including particulate matter (PM/PN).
Summary of the Invention
According to the present invention there is provided a fuel composition comprising:
(a) a gasoline base fuel suitable for use in a spark ignition internal combustion engine; and
(b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and
(c) a tetraalkylethane compound having the formula (I): ex, ex, I I Ar“C- C—Ar ex, cXj wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen atom.
It has been surprisingly found that the fuel compositions of the present invention provide improved power output as reflected in increased Pmax, as well as reduced burn duration of the fuel. Further the fuel
compositions of the present invention exhibit excellent acceleration, energy efficiency and fuel economy.
According to another aspect of the present invention there is provided a use of a liquid fuel composition for improving power output of an internal combustion engine,wherein the liquid fuel composition comprises:
(a) a gasoline base fuel suitable for use in a spark ignition internal combustion engine; and
(b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein the polybutene is a high reactivity polybutene wherein greater than 30% of the polymer molecules in the polyisobutylene polymer have a terminal vinylidene group; and
(c) a tetraalkylethane compound having the formula (I): ex, ex,
I I
Ar~C- -C—Ar
I I
CXj ex, wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX2 group is a hydrogen atom.
According to another aspect of the present invention there is provided a method of increasing the power output of a spark ignition internal combustion engine wherein the method comprises adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene has a number average molecular weight in the
range from 200 to 10,000 g/mol, preferably wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and wherein the tetraalkylethane compound has the formula
(I):
wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX2 group is a hydrogen atom, and combusting the fuel composition in the spark ignition internal combustion engine.
According to yet another aspect of the present invention there is provided a method of reducing the burn duration of a liquid fuel composition in an internal combustion engine, wherein the method comprises adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene has a number average molecular weight in the range from 200 to 10,000 g/mol, preferably wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and wherein the tetraalkylethane compound has the formula (I):
wherein Ar represents an aryl group and each X is
independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen atom, and combusting the fuel composition in the spark ignition internal combustion engine Brief Description of the Drawings
Figure 1 is a graphical representation of the Pmax measurements for Example 1 and its reference base fuel.
Figure 2 is a graphical representation of the Pmax measurements for Examples 2-4 and their reference base fuel.
Figure 3 is a graphical representation of the Pmax measurements for Examples 5-13 and their reference base fuel.
Figure 4 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 5-13) and it's base fuel control at 1300 HL , IGN = 1 (IGN = ignition time).
Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel.
Figure 6 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 14-27) and the base fuel control at 1300 rpm, 15 IMEP, IGN at TDC. Detailed Description of the Invention
The term "power output" as used herein refers to the amount of resistance power required to maintain a fixed speed at wide open throttle conditions in Chassis Dynamometer testing.
The term 'Pmax' as used herein refers to the direct
measurement of the force generated by decomposition of the fuel.
According to the present invention, there is provided a method of improving the power output of an internal combustion engine. Also, according to the present invention, there is a method of improving the Pmax of an internal combustion engine. In the context of these aspects of the present invention, the term "improving" embraces any degree of improvement. The improvement may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more, even more especially 5% or more, of the power output or Pmax provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention. The improvement in power output or Pmax may even be as high as 10% of the power output or Pmax provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
The combination of a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound may also be used to improve the acceleration of an internal combustion engine. The term "acceleration" as used herein refers to the amount of time required for the engine to increase in speed between two fixed speed conditions in a given gear. In the context of this aspect of the invention, the term "improving" embraces any degree of improvement, and may be improved by the same percentages as the power and or
Pmax is increased above.
In accordance with the present invention, the power output and acceleration provided by a fuel composition may be determined in any known manner for instance using the standard test methods as set out in SAE Paper 2005- 01-0239 and SAE Paper 2005-01-0244.
The term 'burn duration' as used herein means the time required (in engine crank angle degrees) for combustion to progress from 10% to 90% (referred to as Al 10-90 in the Examples below). The term Al 50-90 is also used in relation to burn duration and means the time required (in engine crank angle degrees) for combustion to progress from 50% to 90%.
According to the present invention, there is provided a method of reducing the burn duration of a gasoline fuel composition wherein the method comprises adding a polybutene polymer and a tetraalkylethane compound to the gasoline fuel composition, wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol and wherein the tetraalkylethane compound has the formula (I):
Ar“C- C—Ar
CX, CXj wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen atom, and combusting the fuel composition in the spark ignition internal combustion engine
In accordance with the present invention, the burn
duration of a fuel composition may be determined in any known manner, for instance using the test method disclosed in the Examples section hereinbelow.
In the context of this aspect of the invention, the term "reducing the burn duration" embraces any degree of reduction. The reduction may for instance be 0.05% or more, preferably 0.1% or more, more preferably 0.2% or more, even more preferably 0.5% or more, especially 1% or more, more especially 2% or more and even more especially 4% or more, or 5% or more reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention. The reduction in burn duration may even be as high as a 10% reduction of the burn duration provided by an analogous fuel formulation, prior to adding a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound to it in accordance with the present invention.
The term "flame speed" or 'laminar flame speed' (LES) refers to laminar burning velocity. LES is a fundamental measure of flame propagation rate without complication of mixing dynamics. However, in an engine, mixing dynamics play a role, so the measured flame speed is referred to as 'burn rate' and 'burn duration'. The terms 'burn rate' and 'burn duration' can also used herein interchangeably with 'flame speed'. Laminar Burning Velocity (LBV) is a fundamental property of a chemical component. It is defined as the rate (normal to the flame front, under laminar flow conditions) at which unburnt gas propagates to the flame front and reacts to form products.
The flame speed of a fuel composition may be determined in any known manner, for instance measurement of LFS can be performed using any one of the following three methods:
1. Stagnation flame method (up to 5-7 atm)
2. Spherically expanding method, either constant pressure or constant volume (up to 60-80 atm)
3. The heat flux method (up to 5 atm or so).
All three of these methods are described in the review publication: Egolfopoulos, F.N., Hansen, N., Ju, Y., Kohse-Hbinghaus, K., Law, C.K., and Qi, F. "Advances and challenges in laminar flame experiments and implications for combustion chemistry",Progress in Energy and Combustion Science 43 (2014) 36-67, https://doi.Org/10.1016/j.pecs.2014.04.004.
The following method for measuring flame speed in a constant volume combustion chamber (spherical bomb), ref Gillespie, L.L., M.; Sheppard, C.G.; Wooley, R, Aspects of laminar and turbulent burning velocity relevant to spark ignition engines, Journal of the Society of Automotive Engineers, 2000 (2000-01-0192).
The following method for measuring flame speed uses a net pressure method: Mittal, M., Zhu, G. and Schock H., 'Fast mass-fraction-burned calculation using the net pressure method for real-time applications', Proc. Instn Meeh Engrs, Part D: J. Automobile Engineering 223 (3) (2009): 389-394.
The liquid fuel composition of the present invention comprises a base fuel suitable for use in an internal combustion engine, a low molecular weight, preferably high reactivity, polybutene and a tetraalkylethane compound. Typically, the base fuel suitable for use in an internal combustion engine is a gasoline or a diesel
fuel, and therefore the liquid fuel composition of the present invention is typically a gasoline composition or a diesel fuel composition. Preferably, the base fuel is a gasoline base fuel.
The polybutene for use herein is preferably a high reactivity polybutene. A high reactivity polybutene is a polybutene having a relatively high proportion, i.e. greater than 30%, of polymer molecules having a terminal vinylidene group. The term 'polybutene' as used herein includes polymers made from pure or substantially pure 1- butene or isobutene, and polymers made from mixtures of two or all three of 1-butene, 2-butene and isobutene, as well as including polymers containing minor amounts, preferably less than 10% by weight, more preferably less than 5% by weight, of C2, C3, and C5 and higher olefins as well as diolefins. In a preferred embodiment, the polybutene is a polyisobutene (also referred to as 'polyisobutylene') preferably wherein at least 90% by weight, more preferably at least 95% by weight, of the polymer is derived from isobutene.
In a particularly preferred embodiment, the polybutene is a high reactivity polyisobutylene.
In one embodiment, the high reactivity polybutene has greater than 40% of polymer molecules having a terminal vinylidene group.
In another embodiment, the high reactivity polybutene polymer has greater than 50% of polymer molecules having a terminal vinylidene group.
In a preferred embodiment, the high reactivity polybutene has more than 85% of its double bonds located in the terminal position of the molecule.
The high reactivity polybutene polymer for use herein preferably has a molecular mass distribution of
1.5 or greater, preferably 1.6 or greater, more preferably 1.7 or greater, even more preferably 1.8 or greater.
The polybutene polymer is present at a level of from 500ppm to 5000ppm. In one embodiment, the polybutene polymer is present at a level of from 1000 ppm to 5000 ppm. In another embodiment the polybutene polymer is present at a level of from 2500 to 5000 ppm, by weight of the fuel composition. Examples of preferred levels of polybutene include lOOOppm, 2500ppm and 5000ppm, by weight of the fuel composition.
One or more polybutene polymer can be used in the fuel compositions herein. When more than one polybutene polymer is used herein, the total level of polybutene polymer is the same as the ranges given in the previous paragraph.
The polybutene polymer for use herein is a low molecular weight polybutene polymer. As used herein the term 'low molecular weight polybutene' means a polybutene polymer having a number average molecular weight (Mn) in the range from 200 to 10,000 g/mol, preferably from 500 to 5000 g/mol, more preferably from 1000 to 5000 g/mol. In one embodiment of the invention, the polybutenes, preferably high reactivity polybutenes, for use herein have a number average molecular weight (Mn) from 1000 to 2300 g.mol. In another embodiment of the invention, the polybutenes for use herein have a number average molecular weight (Mn) from 2300 to 5000 g/mol. The number average molecular weight of the polybutene polymer can be determined using Gel Permeation Chromatography.
The high reactivity polybutenes for use herein may be bioderived or non-bioderived. In one embodiment of the invention, the polybutene is a low molecular weight,
high reactivity polyisobutylene which is derived from
100% renewable feedstock.
The high reactivity polybutenes for use herein preferably contain less than 1 mg/kg of chlorine.
In one embodiment, the high reactivity polybutene polymer for use herein has a kinematic viscosity at 100°C of 190 mm2/s or greater, preferably in the range of 190 mm2/s to 1500 mm2/s, more preferably in the range from 430 to 1500 mm2/s.
A preferred high reactivity polybutene for use herein has an alpha olefin content of greater than 85%.
Suitable high reactivity polybutenes for use herein include those commercially available from BASF under the tradename Glissopal (RTM) such as Glissopal (RTM) 1000, Glissopal (RTM) 1300 and Glissopal (RTM) 2300.
Glissopal (RTM) 1000 has a number average molecular weight (Mn) of 1000 g/mol, a molecular mass distribution (Mw/Mn) of 1.6, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm2/s and a chlorine content of less than 1 mg/kg.
Glissopal (RTM) 1300 has a number average molecular weight (Mn) of 1300 g/mol, a molecular mass distribution (Mw/Mn) of 1.7, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm2/s and a chlorine content of less than 1 mg/kg.
Glissopal (RTM) 2300 has a number average molecular weight (Mn) of 2300, a molecular mass distribution (Mw/Mn) of 1.6, an alpha olefin content of greater than 85%, a kinematic viscosity at 100°C of 190 mm2/s and a chlorine content of less than 1 mg/kg.
Also suitable for use herein are Glissopal (RTM) 1000, 1300 and 2300 BMBcert (TM) which are low molecular weight, highly reactive polyisobutenes derived from 100%
renewable feedstock, commercially available from BASF.
The polybutene polymer may be blended together with any other additives in addition to the tetraalkylethane compound e.g. additive performance package(s) to produce an additive blend. The additive blend is then added to a base fuel to produce a liquid fuel composition.
The tetraalkylethane compound used herein is a compound having the formula (I):
wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 saturated or unsaturated alkyl group, (CH2)nOH, (CH2)nNH2, wherein n is in the range from 1 to 9, preferably in the range from 1 to 6, more preferably in the range from 1 to 4, even more preferably in the range from 1 to 3, provided that at least one of the X groups in each CX3 group is a hydrogen atom.
Preferably, at least two of the X groups in each CX3 group is a hydrogen atom.
In an especially preferred embodiment, three of the X groups in each CX3 group is a hydrogen atom.
Preferably, the Ar of the tetraalkylethane compound is a substituted or unsubstituted aromatic group, such as a phenyl, biphenyl, naphthyl, thienyl or anthracyl. More preferably, Ar is an unsubstituted phenyl group. This means that for the preparation of the preferred compound of formula (I) it is possible to start out with cumene, which is commercially available. Starting with cumene, dicumene can be prepared by several known methods, as
described in US4,072,811. Preferably, each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated or unsaturated C1-C6, more preferably C1-C3, alkyl group, provided that at least one of the X groups in each CX3 group is a hydrogen atom. More preferably, each X group is independently selected from a hydrogen atom and an unsubstituted, straight chain or branched, saturated C1-C6, preferably C1-C3, alkyl group, provided that at least one of the X groups in each CX3 group is a hydrogen atom. In one embodiment, each X group is independently selected from a hydrogen atom, and an unsubstituted straight chain, saturated C1-C6, preferably C1-C3, alkyl group, especially methyl, ethyl and propyl. Examples of suitable tetraalkylethane compounds of Formula (I) include:
In one embodiment herein the tetralkylethane compound is 1,1'(1,1,2,2-tetramethyl-l,1-ethanediyl)bis- benzene Dicumene is commercially available
from Aldrich and various other chemical suppliers. The tetraalkylethane compound is preferably present in the fuel composition at a level from 30ppm to 10 wt%, preferably from 100ppm to 5 wt%, more preferably from 100ppm to 1 wt%, even more preferably from 100ppm to 5000ppm. In one embodiment, the tetraalkylethane is present at a level from 313ppm to 5000ppm, by weight of the fuel composition. The tetraalkylethane compound may be blended together with any other additives in addition to the polybutene polymer e.g. additive performance package(s) to produce an additive blend. The additive blend is then added to a base fuel to produce a liquid fuel composition. The amount of performance package(s) in the additive blend is preferably in the range of from 0.1 to 99.8 wt%, more preferably in the range of from 5 to 50 wt%, by weight of the additive blend. Preferably, the amount of the performance package present in the liquid fuel composition of the present invention is in the range of 15 ppmw (parts per million by weight) to 10 %wt, based on the overall weight of the liquid fuel composition. More preferably, the amount of the performance package present in the liquid fuel composition of the present invention additionally accords with one or more of the parameters (i) to (xv) listed below: (i) at least 100 ppmw (ii) at least 200 ppmw (iii) at least 300 ppmw (iv) at least 400 ppmw (v) at least 500 ppmw
(vi) at least 600 ppmw (vii) at least 700 ppmw (viii) at least 800 ppmw (ix) at least 900 ppmw (x) at least 1000 ppmw (xi) at least 2500ppmw (xii) at most 5000ppmw (xiii) at most 10000 ppmw (xiv) at most 2 %wt. (xv) at most 5 %wt. A further preferred additive for use in the fuel compositions herein, in combination with the tetralkylethane compound and the polybutene polymer is an alkylbenzene compound having the f n each R1-R6 gr R1 R2ormula (II) wherei R R65 R4 R3ently selected from hydrogen and a C1-C6
alkyl group, wherein at least one of the R1-R6 groups is a C1-C6 alkyl group. In preferred embodiments herein, three R1-R6 groups in the alkylbenzene compound are independently selected from a C1-C6 alkyl group. In one embodiment herein the alkylbenzene compound is a trimethylbenzene compound. In another embodiment, the alkykbenzene compound is 1,3,5-trimethylbenzene. 1,3,5-trimethylbenzene is commercially available from Aldrich and other chemical suppliers. In another embodiment, the alkylbenzene compound is a mixture of trimethylbenzene isomers (known as mesitylene).
The alkylbenzene compound is preferably present in the fuel composition at a level from 30ppm to 2 wt%, preferably from lOOppm to 1 wt%, more preferably from lOOppm to 5000ppm, even more preferably from 500ppm to 2000ppm, by weight of the fuel composition.
In one embodiment, the alkylbenzene compound, the tetraalkylethane compound and the polybutene polymer may be blended together with any other additives e.g. additive performance package(s) to produce an additive blend. The additive blend is then added to a base fuel to produce a liquid fuel composition.
In the liquid fuel compositions of the present invention, if the base fuel used is a gasoline, then the gasoline may be any gasoline suitable for use in an internal combustion engine of the spark-ignition (petrol) type known in the art, including automotive engines as well as in other types of engine such as, for example, off road and aviation engines. The gasoline used as the base fuel in the liquid fuel composition of the present invention may conveniently also be referred to as 'base gasoline'.The gasoline may also comprise various levels of bio-components and bio-streams at any level while maintaining appropriate analytical specifications. The bio-components may come from any biomass conversion processes including variations of uncatalyzed and catalyzed biomass pyrolyses, hydro-thermal liquefaction, non-thermal biomass conventions such as microbe catalyzed biochemical processes, etc. Any biomass suitable as feedstock to these processes is ideal.
Gasolines typically comprise mixtures of hydrocarbons boiling in the range from 25 to 230°C (EN- ISO 3405), the optimal ranges and distillation curves typically varying according to climate and season of the
year. The hydrocarbons in a gasoline may be derived by any means known in the art, conveniently the hydrocarbons may be derived in any known manner from straight-run gasoline, synthetically-produced aromatic hydrocarbon mixtures, thermally or catalytically cracked hydrocarbons, hydro-cracked petroleum fractions, catalytically reformed hydrocarbons or mixtures of these.
The specific distillation curve, hydrocarbon composition, research octane number (RON) and motor octane number (MON) of the gasoline are not critical.
Conveniently, the research octane number (RON) of the gasoline may be at least 80, for instance in the range of from 80 to 110, preferably the RON of the gasoline will be at least 90, for instance in the range of from 90 to 110, more preferably the RON of the gasoline will be at least 91, for instance in the range of from 91 to 105, even more preferably the RON of the gasoline will be at least 92, for instance in the range of from 92 to 103, even more preferably the RON of the gasoline will be at least 93, for instance in the range of from 93 to 102, and most preferably the RON of the gasoline will be at least 94, for instance in the range of from 94 to 100 (EN 25164); the motor octane number (MON) of the gasoline may conveniently be at least 70, for instance in the range of from 70 to 110, preferably the MON of the gasoline will be at least 75, for instance in the range of from 75 to 105, more preferably the MON of the gasoline will be at least 80, for instance in the range of from 80 to 100, most preferably the MON of the gasoline will be at least 82, for instance in the range of from 82 to 95 (EN 25163).
Typically, gasolines comprise components selected from one or more of the following groups; saturated
hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and oxygenated hydrocarbons. Conveniently, the gasoline may comprise a mixture of saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and, optionally, oxygenated hydrocarbons.
Typically, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 40 percent by volume based on the gasoline (ASTM D1319); preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 30 percent by volume based on the gasoline, more preferably, the olefinic hydrocarbon content of the gasoline is in the range of from 0 to 20 percent by volume based on the gasoline.
Typically, the aromatic hydrocarbon content of the gasoline is in the range of from 0 to 70 percent by volume based on the gasoline (ASTM D1319), for instance the aromatic hydrocarbon content of the gasoline is in the range of from 10 to 60 percent by volume based on the gasoline; preferably, the aromatic hydrocarbon content of the gasoline is in the range of from 0 to 50 percent by volume based on the gasoline, for instance the aromatic hydrocarbon content of the gasoline is in the range of from 10 to 50 percent by volume based on the gasoline. In one embodiment herein the gasoline base fuel comprises less than 10 vol% of aromatics, based on the total base fuel. In another embodiment herein, the gasoline base fuel comprises less than 2 vol% of aromatics having 9 carbon atoms or greater, based on the total base fuel.
The benzene content of the gasoline is at most 10 percent by volume, more preferably at most 5 percent by volume, especially at most 1 percent by volume based on the gasoline.
The gasoline preferably has a low or ultra low
sulphur content, for instance at most 1000 ppmw (parts per million by weight), preferably no more than 500 ppmw, more preferably no more than 100, even more preferably no more than 50 and most preferably no more than even 10 ppmw.
The gasoline also preferably has a low total lead content, such as at most 0.005 g/1, most preferably being lead free - having no lead compounds added thereto (i.e. unleaded).
When the gasoline comprises oxygenated hydrocarbons, at least a portion of non-oxygenated hydrocarbons will be substituted for oxygenated hydrocarbons (match-blending) or simply added to the fully formulated gasoline (splash- blending). The oxygenate content of the gasoline may be up to 85 percent by weight (EN 1601) (e.g. ethanol per se) based on the gasoline. For example, the oxygenate content of the gasoline may be up to 35 percent by weight, preferably up to 25 percent by weight, more preferably up to 10 percent by weight. Conveniently, the oxygenate concentration will have a minimum concentration selected from any one of 0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 percent by weight, and a maximum concentration selected from any one of 12, 8, 7.2, 5, 4.5, 4.0, 3.5, 3.0, and 2.7 percent by weight.
Examples of oxygenated hydrocarbons that may be incorporated into the gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen containing heterocyclic compounds. Preferably, the oxygenated hydrocarbons that may be incorporated into the gasoline are selected from alcohols (such as methanol, ethanol, propanol, 2- propanol, butanol, tert-butanol, iso-butanol and 2- butanol), ethers (preferably ethers containing 5 or more
carbon atoms per molecule, e.g., methyl tert-butyl ether and ethyl tert-butyl ether) and esters (preferably esters containing 5 or more carbon atoms per molecule); a particularly preferred oxygenated hydrocarbon is ethanol.
When oxygenated hydrocarbons are present in the gasoline, the amount of oxygenated hydrocarbons in the gasoline may vary over a wide range. For example, gasolines comprising a major proportion of oxygenated hydrocarbons are currently commercially available in countries such as Brazil and U.S.A., e.g. ethanol per se and E85, as well as gasolines comprising a minor proportion of oxygenated hydrocarbons, e.g. E10 and E5. Therefore, the gasoline may contain up to 100 percent by volume oxygenated hydrocarbons. E100 fuels as used in Brazil are also included herein. Preferably, the amount of oxygenated hydrocarbons present in the gasoline is selected from one of the following amounts: up to 85 percent by volume; up to 70 percent by volume; up to 65 percent by volume; up to 30 percent by volume; up to 20 percent by volume; up to 15 percent by volume; and, up to
10 percent by volume, depending upon the desired final formulation of the gasoline. Conveniently, the gasoline may contain at least 0.5, 1.0 or 2.0 percent by volume oxygenated hydrocarbons.
Examples of suitable gasolines include gasolines which have an olefinic hydrocarbon content of from 0 to 20 percent by volume (ASTM D1319), an oxygen content of from 0 to 5 percent by weight (EN 1601), an aromatic hydrocarbon content of from 0 to 50 percent by volume (ASTM D1319) and a benzene content of at most 1 percent by volume.
Also suitable for use herein are gasoline blending components which can be derived from sources other than
crude oil, such as low carbon gasoline fuels from either biomass or CO2, and blends thereof which each other or with fossil-derived gasoline streams and components. Suitable examples of such fuels include:
1) Biomass derived: a. Straight run bio-naphthas from hydrodeoxygenation of biomass, and b. cracked and/or isomerized products of syn-wax (biomass gasification to syngas (CO/H2) then to syn-wax by the Fischer-Tropsch (FT) process, which is then hydrocracked/hydroisomerized to yield a slate of products including cuts in the gasoline distillation range.
2) CO2 derived: a. CO2 + H2 syngas (CO/H2) by modified water/gas shift reaction, then to syn-wax by the FT process), which is then hydrocracked/hydroisomerized to yield a slate of products including cuts in the gasoline distillation range.
3) Methanol derived: a. Biomass gasification to syngas (CO/H2), then to Methanol and then gasoline by the MTG process (MTG is 'methanol-to-gasoline' process). To reduce the carbon intensity of the fuel further, the H2 used in all processes would be renewable (green) H2 from electrolysis of water using renewable electricity such as from wind and solar.
Particularly suitable for use herein are gasoline blending components which can be derived from a biological source. Examples of such gasoline blending components can be found in W02009/077606, W02010/028206, WO2010/000761, European patent application nos. 09160983.4, 09176879.6, 09180904.6, and US patent application serial no. 61/312307.
Whilst not critical to the present invention, the base gasoline or the gasoline composition of the present invention may conveniently include one or more optional fuel additives, in addition to the low molecular weight, preferably high reactivity, polybutene and the tetraalkylethane compound. The concentration and nature of the optional fuel additive(s) that may be included in the base gasoline or the gasoline composition of the present invention is not critical. Non-limiting examples of suitable types of fuel additives that can be included in the base gasoline or the gasoline composition of the present invention include anti-oxidants, corrosion inhibitors, detergents, dehazers, antiknock additives, metal deactivators, valve-seat recession protectant compounds, dyes, solvents, carrier fluids, diluents and markers. Examples of suitable such additives are described generally in US Patent No. 5,855,629.
Conveniently, the fuel additives can be blended with one or more solvents to form an additive concentrate, the additive concentrate can then be admixed with the base gasoline or the gasoline composition of the present invention.
The (active matter) concentration of any optional additives present in the base gasoline or the gasoline composition of the present invention is preferably up to 1 percent by weight, more preferably in the range from 5 to 2000 ppmw, advantageously in the range of from 300 to 1500 ppmw, such as from 300 to 1000 ppmw.
Further customary additives for use in gasolines are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids, said salts tending to form films, or of heterocyclic aromatics for nonferrous metal corrosion protection; dehazers; anti-knock additives;
metal deactivators; solvents; carrier fluids; diluents; antioxidants or stabilizers, for example based on amines such as phenyldiamines, e.g. p-phenylenediamine, N,N'-di- sec-butyl-p-phenyldiamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxy- phenylpropionic acid; anti-static agents; metallocenes such as ferrocene; methylcyclopentadienylmanganese tricarbonyl; lubricity additives, such as certain fatty acids, alkenylsuccinic esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and also dyes (markers). Suitable such additives are disclosed in US Patent No. 5,855,629. Amines may also be added, if appropriate, for example as described in WO 03/076554. Optionally anti valve seat recession additives may be used such as sodium or potassium salts of polymeric organic acids.
The gasoline compositions herein can also comprise a detergent additive. Suitable detergent additives include those disclosed in W02009/50287, incorporated herein by reference.
Preferred detergent additives for use in the gasoline composition herein typically have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (Mn) of from 85 to 20000 and at least one polar moiety selected from:
(Al) mono- or polyamino groups having up to 6 nitrogen atoms, of which at least one nitrogen atom has basic properties;
(A6) polyoxy-Cg- to -C4-alkylene groups which are terminated by hydroxyl groups, mono- or polyamino groups, in which at least one nitrogen atom has basic properties, or by carbamate groups;
(A8) moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or
(A9) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.
The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubility in the base fluid, has a number-average molecular weight (Mn) of from 85 to 20000, especially from 113 to 10000, in particular from 300 to 5000. Typical hydrophobic hydrocarbon radicals, especially in conjunction with the polar moieties (Al), (A8) and (A9), include polyalkenes (polyolefins), such as the polypropenyl, polybutenyl and polyisobutenyl radicals each having Mn of from 300 to 5000, preferably from 500 to 2500, more preferably from 700 to 2300, and especially from 700 to 1000.
Non-limiting examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Al) are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn of from 300 to 5000. When polybutene or polyisobutene having predominantly internal double bonds (usually in the beta and gamma position) are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used
here for the amination may be, for example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylene- triamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on polypropene are described in particular in WO-A-94/24231. Further preferred additives comprising monoamino groups (A1) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization of from 5 to 100, with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946. Further preferred additives comprising monoamino groups (A1) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262. Additives comprising polyoxy-C2-C4-alkylene moieties (A6) are preferably polyethers or polyetheramines which are obtainable by reaction of C2- to C60-alkanols, C6- to C30-alkanediols, mono- or di-C2-C30-alkylamines, C1-C30- alkylcyclohexanols or C1-C30-alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyether-amines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP- A-356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products
with ammonia.
Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups (A8) are preferably corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by reacting conventional or highly reactive polyisobutene having Mn of from 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene. Of particular interest are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such additives are described in particular in US-A-4849572.
Additives comprising moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines (A9) are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may stem from conventional or highly reactive polyisobutene having Mn of from 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831141.
Preferably, the detergent additive used in the gasoline compositions of the present invention contains at least one nitrogen-containing detergent, more preferably at least one nitrogen-containing detergent containing a hydrophobic hydrocarbon radical having a number average molecular weight in the range of from 300 to 5000. Preferably, the nitrogen-containing detergent is selected from a group comprising polyalkene monoamines, polyetheramines, polyalkene Mannich amines
and polyalkene succinimides. Conveniently, the nitrogen- containing detergent may be a polyalkene monoamine.
In the above, amounts (concentrations, % vol, ppmw, % wt) of components are of active matter, i.e. exclusive of volatile solvents/diluent materials.
The liquid fuel composition of the present invention can be produced by admixing the essential low molecular weight, preferably high reactivity, polybutene polymer and the essential tetraalkylethane compound with a gasoline base fuel suitable for use in an internal combustion engine. Since the base fuel to which the essential fuel additive is admixed is a gasoline, then the liquid fuel composition produced is a gasoline composition.
It has surprisingly been found that the use of a combination of a low molecular weight, preferably high reactivity, polybutene having a number average molecular weight of from 500 to 10,000 g/mol and a tetraalkylethane compound, provides synergistic benefits in terms of improved power and increased Pmax of an internal combustion engine being fuelled by the liquid fuel composition containing said polybutene, relative to the internal combustion engine being fuelled by the liquid base fuel. In a preferred embodiment herein, an improvement in power can be observed at low load and low speed conditions (such as at 1300 rpm and 11.5 bar) as well as at high load and high speed conditions (such as at 3300 rpm and 12.4 bar).
It has also surprisingly been found that the the use of a combination of a low molecular weight, preferably high reactivity, polybutene having a number average molecular weight of from 500 to 10,000 g/mol and a tetraalkylethane compound provides synergistic benefits
in terms of reduced burn duration of the liquid fuel composition containing said polybutene, relative to the internal combustion engine being fuelled by the liquid base fuel.
Preferably, the internal combustion engine herein is a spark ignition internal combustion engine operating in either PFI (Port fuel injection) or GDI (gasoline direct injection) mode.
The present invention will be further understood from the following examples. Unless otherwise stated, all amounts and concentrations disclosed in the examples are based on weight of the fully formulated fuel composition.
Examples
Examples 1-13
The goal of these experiments was to screen a set of additives with potential for combustion enhancing properties using the gasoline single cylinder engine (GSCE) in PFI mode. Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
A number of fully formulated fuel compositions are provided below (Examples 1 to 13).
All fuel compositions used an E10 base fuel (containing 10% ethanol) meeting North American maingrade specification ASTM D4814 containing no performance additive. Example 1 used an E10 base fuel having a RON of 92.3, Examples 2-4 used an E10 base fuel having a RON of 96.7 and Examples 5-13 used an E10 base fuel having a RON of 96.5.
High reactivity polyisobutylene (HR-PIB) and/or
dicumene were added into the base fuel at the treat rates indicated in Tables 1 and 2 below. Some of the Examples also included mesitylene, as indicated. Mesitylene is a mixture of trimethylbenzene isomers. Tables 1 and 2 also show the RON and MON values for each fuel formulation.
Table 1
Examples Additives Dose, ppm RON MON RON- wt% MON
E10 base fuel — — 92.3 96.6 5.7 (RON 92.3)
1 PIB 5000/5000 91.3 84.9 6.4
(1000)/dicumene
E10 base fuel — — 96.7 85 11.7 (RON 96.7)
2 dicumene 5000 95 83.9 11.1
3 PIB 5000/5000 94.4 83.4 11
(1000)/dicumene
4 PIB (1000) 5000 96.4 85 11.4
Table 2
Examples Additives Dose, ppm RON MON RON- wt% MON
E10 base fuel — — 96.5 86 10.5 (RON 96.5)
5 dicumene 5000 94.1 84.1 10
Mesitylene 5000
PIB (1000) 5000
6 dicumene 2500 95 84.6 10.4 mesitylene 5000
PIB (1000) 5000
7 dicumene 1250 95.5 85 10.5
Mesitylene 2500
PIB (1000) 5000
8 Dicumene 625 95.8 85.5 10.3 mesitylene 1250
PIB (1000) 2500
9 Dicumene 625 95.8 85.6 10.2
PIB (1000) 2500
10 Dicumene 313 96 85.8 10.2
PIB (1000) 1000
11 PIB (1000) 5000 96.5 86 10.5
12 PIB (1000) 2500 96.4 86.1 10.3
13 PIB (1000) 1000 96.4 86.2 10.2
Test Conditions
The engine used for these experiments was the Gasoline single cylinder engine in PFI mode. This engine was manufactured by AVL and based on the EA8882.OL Audi TFSI/VW TSI (Euro 6). The single cylinder bench engine details are shown in Table 3 below.
Table 3
Parameter: Details:
Manufacturer AVL
Displaced Volume 454 cm3
Cylinders 1
Stroke 86 mm
Bore 82 mm
Compression ratio Variable 8-12, (10:1 chosen)
Number of valves 2 inlet; 2 outlet
Maximum engine speed 5000 rpm (3300 rpm chosen)
Aspiration Slightly Boosted (max 2.5 bar absolute)
Injection PFI (solenoid injector)
Other IMEP up to 25 bar, Max. peak pressure 130 bar continuous
The engine test conditions are detailed below in
Table 4
Table 4
Engine Speed IMEP Intake Intake Exhaust Fuel Fuel test [RPM] [Bar] pressure temp. back pressure temp conditions [mbara] [°C] pressure [bar] [°C] [mbara]
1300HL 1300 11.5 1110 35 1080 3 25
1300ML 1300 8 905 35 1080 3 25
3300HL 3300 12.4 1205 35 1850 3 25
The test protocol below was run with base fuel and one test fuel (one of Examples 1-13) per day:
• Warm up engine and line out on base fuel • Run baseline spark sweep: 1300 ML, HL, 3000 ML (ML = medium load; HL = high load)
• Switch to test fuel and flush 30 litre
• Test: spark sweep at three different conditions (1300 rpm, IMEP: 11.5 bar and 8 bar; and 3300 rpm, IMEP: 12.4 bar)
• End.
Each test fuel blend was screened twice, once in each of two randomized loops. Average maximum pressure (Pmax) measurements were taken and the results are shown in Figures 1-4.
Figure 1 is a graphical representation of the Pmax measurements for Example 1 and its reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
Figure 2 is a graphical representation of the Pmax measurements for Examples 2-4 and their reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
Figure 3 is a graphical representation of the Pmax measurements for Examples 5-13 and their reference base fuel (the Example number being on the x axis and Pmax being on the y axis).
Figure 4 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend and it's base fuel control at 1300 HL , IGN = 1 (IGN = ignition time). In Figure 4, the Example number is on the x axis and the average % difference in burn duration and average % difference in Pmax is on the y axis. Examples 14-27
The goal of these experiments was to screen a set of additives with potential for combustion enhancing properties using the gasoline single cylinder engine (GSCE) in GDI mode. Combustion enhancement could be shown in basically two modes: pre-ignition delay (octane
boosting, important for reduced knock at high compression ratio) or flame speed improver (shortened burn duration leading to improved power).
A number of fully formulated fuel compositions are provided below (Examples 14 to 27).
All fuel compositions used an E10 base fuel (containing 10% ethanol) meeting North American maingrade specification ASTM D4814 containing no performance additive having a RON of 96.5. High reactivity polyisobutylene (HR-PIB) and/or dicumene were added into the base fuel at the treat rates indicated in Table 5 below. Some of the Examples also included mesitylene, as indicated. Mesitylene is a mixture of trimethylbenzene isomers. Table 5 also shows the RON and MON values for each fuel formulation.
Table 5
Examples Additives Dose, ppm RON MON RON- wt% MON
E10 base fuel — — 95.7 84.4 11.3 (RON 95.7)
14 PIB (1000) 2500 95.7 84.4 11.3
15 Mesitylene 625 95.8 84.4 11.4
PIB (1000) 1250
16 Mesitylene 1250 96 84.4 11.6
PIB (1000) 1250
17 Mesitylene 1250 95.9 84.5 11.4
PIB (1000) 2500
18 dicumene 625 95.3 84.3 11
PIB (1000) 1250
19 dicumene 625 95.2 84.4 10.8
Mesitylene 625
20 dicumene 625 95.3 84.4 10.9
PIB (1000) 2500
21 dicumene 625 95.3 84.3 11
Mesitylene 1250
PIB (1000) 1250
22 dicumene 625 95.3 84.2 11.1
Mesitylene 1250
PIB (1000) 2500
23 dicumene 1250 95 84 11
24 dicumene 1250 95 83.8 11.2
PIB (1000) 2500
25 dicumene 1250 95 84.1 10.9
Mesitylene 625
PIB (1000) 1250
26 dicumene 1250 95 83.8 11.2
Mesitylene 625
PIB (1000) 2500
27 dicumene 1250 95 83.9 11.1
Mesitylene 1250
Test Conditions
The engine used for these experiments was the Gasoline single cylinder engine in GDI mode. This engine was manufactured by AVL and based on the EA8882.0L Audi
TFSI/VW TSI (Euro 6). The single cylinder bench engine details are shown in Table 6 below.
Table 6
Parameter: Details:
Manufacturer AVL
Displaced Volume 454 cm3
Cylinders 1
Stroke 86 mm
Bore 82 mm
Compression ratio Variable 8-12, (10:1 chosen)
Number of valves 2 inlet; 2 outlet
Maximum engine speed 5000 rpm (3300 rpm chosen)
Aspiration Slightly Boosted (max 2.5 bar absolute)
Injection GDI mode
Other IMEP up to 25 bar, Max. peak pressure 130 bar continuous
The engine test conditions are detailed below in
Table 7
Table 7
Engine Speed IMEP Intake Intake Exhaust Fuel Fuel test [RPM] [Bar] pressure temp. back pressure temp conditions [mbara] [°C] pressure [bar] [°C] [mbara]
1300HL 1300 15 1300 40 25 200 25
2000ML 2000 13.5 1200 40 45 200 25
3300HL 3300 16.2 1400 40 200 200 25
The test protocol below was run with base fuel and one test fuel (one of Examples 14-27) per day:
• Warm up engine and line out on base fuel
• Run baseline spark sweep: 1300 ML, 2000 ML and 3000 ML (ML = medium load; HL = high load)
• Switch to test fuel and flush 30 litre
• Test: spark sweep at three different conditions (1300 rpm, IMEP: 15 bar; 2000 rpm, IMEP: 13.5 bar; and 3300 rpm, IMEP: 16.2 bar)
• End.
Each test fuel blend was screened twice, once in each of two randomized loops. Average maximum pressure (Pmax) measurements were taken and the results are shown in Figures 5 and 6.
Figure 5 is a graphical representation of the Pmax measurements for Examples 14-27 and their reference base fuel. In Figure 5, the Example number is on the x axis and the Pmax is on the y axis).
Figure 6 shows the average % difference in Pmax and average % difference in burn duration (Al 10-90) between the test blend (Examples 14-27) and the base fuel control at 1300 rpm, 15 IMEP, IGN at TDC. In Figure 6, the Example number is on the x axis and the average % difference in burn duration and average % difference in Pmax is on the y axis. Discussion
Use of a combination of dicumene and HR-PIB have been found to provide increased Pmax (related to increased power) in the engine tests of the Examples at various engine conditions, i.e. at both low speed/low load and high load/high speed conditions. This demonstrates that the fuel formulations of the present invention can be
used both for retail customers and for motor sports applications.
Claims
1. Fuel composition comprising:
(a) a gasoline base fuel suitable for use in a spark ignition internal combustion engine; and
(b) a polybutene polymer; wherein the polybutene polymer has a number average molecular weight in the range from 200 to 10,000 g/mol and wherein greater than 30% of the polymer molecules in the polybutene polymer have a terminal vinylidene group; and
(c) a tetraalkylethane compound having the formula (I):
5
Ar ■C- C—-Ar
I I
CXj CX; wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX2 group is a hydrogen atom.
2. Fuel composition according to Claim 1 wherein greater than 40% of the polymer molecules in the polybutene polymer have a terminal vinylidene group.
3. Fuel composition according to Claim 1 or 2 wherein greater than 50% of the polymer molecules in the polybutene polymer have a terminal vinylidene group.
4. Fuel composition according to any of Claims 1 to 3 wherein the polybutene polymer has a number average molecular weight in the range from 500 to 5,000 g/mol.
5. Fuel composition according to any of Claims 1 to 4 wherein the polybutene polymer has a number average
molecular weight in the range from 1000 to 2300 g/mol.
6. Fuel composition according to any of Claims 1 to 5 wherein the polybutene polymer is a polyisobutylene polymer.
7 . Fuel composition according to any of Claims 1 to 6 wherein the polybutene polymer is present at a level from 1000 ppm to 5000 ppm, by weight of the fuel composition.
8 . Fuel composition according to any of Claims 1 to 7 wherein the tetraalkylethane compound is present at a level from 200 ppm to 5000 ppm, by weight of the fuel composition.
9. Fuel composition according to any of Claims 1 to 8 wherein Ar of the tetraalkylethane compound is a substituted or unsubstituted aromatic group selected from phenyl, biphenyl, naphthyl, thienyl or anthracyl.
10. Fuel composition according to any of Claims 1 to 9 wherein Ar is an unsubstituted phenyl group.
11. Fuel composition according to any of Claims 1 to 10 wherein each X is independently selected from a hydrogen atom, unsubstituted, straight chain or branched Ci-Ce alkyl group, provided that at least one of the X groups in each CX3 group is a hydrogen atom.
12. Fuel composition according to any of Claims 1 to 11 wherein the tetralkylethane compound is 1,1'(1,1,2,2- tetramethyl-1,1-ethanediyl)bis-benzene.
13. Use of a liquid fuel composition for improving power output of an internal combustion engine,wherein the liquid fuel composition comprises:
(a) a gasoline base fuel suitable for use in a spark ignition internal combustion engine;
(b) a polybutene polymer; wherein the polybutene polymer has a number average
molecular weight in the range from 200 to 10,000 g/mol, and preferably wherein the polybutene is a high reactivity polybutene wherein greater than 30% of the polymer molecules in the polyisobutylene polymer have a terminal vinylidene group; and
(c) a tetraalkylethane compound having the formula (I): ex, ex, I I Ar“C- C—Ar ex, cXj wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX2 group is a hydrogen atom.
14. A method of increasing the power output of a spark ignition internal combustion engine wherein the method comprises adding a polybutene and a tetraalkylethane compound to a gasoline base fuel to produce a gasoline fuel composition, wherein the polybutene polymer is added at a level from 1000 ppm to 5000 ppm by weight of the gasoline fuel composition, and wherein the tetraalkylethane compound is added at a level from 200 ppm to 5000 ppm by weight of the gasoline fuel composition, wherein the polybutene has a number average molecular weight in the range from 200 to 10,000 g/mol and preferably wherein the polybutene is a high reactivity polybutene wherein greater than 30% of the polymer molecules in the polyisobutylene polymer have a terminal vinylidene group and wherein the tetraalkylethane compound has the formula (I):
CX, exJ
I ■ I
Ar““C- C"—Ar
I I
CX, exJ wherein Ar represents an aryl group and each X is independently selected from a hydrogen atom, substituted or unsubstituted, straight chain or branched C1-C12 alkyl group, (CH2)nOH or (CH2)nNH2, wherein n is in the range of 1 to 9, provided that at least one of the X groups in each CX3 group is a hydrogen atom, and combusting the fuel composition in the spark ignition internal combustion engine.
15. Method according to Claim 14 wherein the spark ignition internal combustion engine operates in PFI or GDI mode.
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