EP0476197A1 - Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu - Google Patents
Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu Download PDFInfo
- Publication number
- EP0476197A1 EP0476197A1 EP90310323A EP90310323A EP0476197A1 EP 0476197 A1 EP0476197 A1 EP 0476197A1 EP 90310323 A EP90310323 A EP 90310323A EP 90310323 A EP90310323 A EP 90310323A EP 0476197 A1 EP0476197 A1 EP 0476197A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- soluble
- compositions
- fuels
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 124
- 239000000446 fuel Substances 0.000 title claims abstract description 119
- 239000000654 additive Substances 0.000 title abstract description 58
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 239000006078 metal deactivator Substances 0.000 claims abstract description 26
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 24
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical group [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 230000009920 chelation Effects 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 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 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002262 Schiff base Substances 0.000 claims description 3
- 150000004753 Schiff bases Chemical class 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000002816 fuel additive Substances 0.000 claims description 2
- 230000003019 stabilising effect Effects 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 abstract description 51
- 239000002270 dispersing agent Substances 0.000 abstract description 29
- 239000004071 soot Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000001473 noxious effect Effects 0.000 abstract description 2
- 239000010802 sludge Substances 0.000 abstract description 2
- -1 Bis(cyclopentadienyl) iron Chemical compound 0.000 description 51
- 125000004432 carbon atom Chemical group C* 0.000 description 32
- 239000003921 oil Substances 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 25
- 238000012360 testing method Methods 0.000 description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000002283 diesel fuel Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 12
- 150000001735 carboxylic acids Chemical class 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 150000001447 alkali salts Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 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 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000010763 heavy fuel oil Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 235000011044 succinic acid Nutrition 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical class OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- 150000002462 imidazolines Chemical class 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 150000003017 phosphorus Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003870 salicylic acids Chemical class 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 2
- GAHCCFASRFYYAQ-UHFFFAOYSA-N C1(C=CC2=CC=CC=C12)[Mn] Chemical compound C1(C=CC2=CC=CC=C12)[Mn] GAHCCFASRFYYAQ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004945 acylaminoalkyl group Chemical group 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
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- 125000004103 aminoalkyl group Chemical group 0.000 description 2
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- 239000003963 antioxidant agent Substances 0.000 description 2
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- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
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- TXQBMQNFXYOIPT-UHFFFAOYSA-N octyl nitrate Chemical class CCCCCCCCO[N+]([O-])=O TXQBMQNFXYOIPT-UHFFFAOYSA-N 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
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- 150000003873 salicylate salts Chemical class 0.000 description 2
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- 241000894007 species Species 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
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- 239000013638 trimer Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- MQCUIYULLYRTPE-UHFFFAOYSA-N 1,4-bis(2-methylpropyl)cyclohexa-2,4-dien-1-ol Chemical compound CC(C)CC1=CCC(O)(CC(C)C)C=C1 MQCUIYULLYRTPE-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UEFBRXQBUTYIJI-UHFFFAOYSA-N decyl nitrate Chemical compound CCCCCCCCCCO[N+]([O-])=O UEFBRXQBUTYIJI-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
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- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- UPCIBFUJJLCOQG-UHFFFAOYSA-L ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium;dibromide Chemical compound [Br-].[Br-].CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC UPCIBFUJJLCOQG-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 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
- 238000001914 filtration Methods 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- AGDYNDJUZRMYRG-UHFFFAOYSA-N hexyl nitrate Chemical class CCCCCCO[N+]([O-])=O AGDYNDJUZRMYRG-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- TUFJPPAQOXUHRI-KTKRTIGZSA-N n'-[(z)-octadec-9-enyl]propane-1,3-diamine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCN TUFJPPAQOXUHRI-KTKRTIGZSA-N 0.000 description 1
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- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 1
- DXYUWQFEDOQSQY-UHFFFAOYSA-N n'-octadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCCN DXYUWQFEDOQSQY-UHFFFAOYSA-N 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
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- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical class [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1814—Chelates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1828—Salts thereof
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- C10L1/2691—Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing compounds
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- 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
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- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- This invention relates to liquid fuel compositions of enhanced properties, particularly as regards combustion and stability characteristics.
- Keszthelyi et al report in Period. Polytech., Chem. Eng., Volume 21 (1 pages 79-93 (1977) that in the combustion of light fuel oils in evaporating burners, 0.025% cyclopentadienyl manganese tricarbonyl was effective for soot reduction. And in Margantsevye Antidetonatory, edited by A. N. Nesmeyanov, Nauka, Moscow, 1971, at pages 192-199, Makhov et al report test work indicating that addition of cyclopentadienyl manganese tricarbonyl to diesel fuel reduces the level of smokiness of the exhaust gases.
- Canadian Patent No. 1,188,891 describes an additive for fuel oils and diesel fuels and other liquid combustibles and motor fuels designed to improve combustion, reduce soot formation and enhance storage stability.
- Such additive is composed of at least one oil-soluble or oil-dispersible organic compound of a transition metal or an alkaline earth metal; and at least one oxidation and polymerisation inhibitor for hydrocarbons stable at temperatures of at least 300 ° C.
- the presence in such fuels of compounds of transition metals such as copper, manganese, cobalt, nickel and iron accelerate fuel deterioration in accelerated stability tests conducted at 149°C in the presence of air.
- Such compounds as MMT, Ferrocene, copper naphthenate, iron naphthenate, and manganese naphthenate are indicated to cause such deterioration in the absence of a high temperature (e.g., 300 C) stabiliser such as heat-stable alkyl phenols, amines, aminophenols, dithiophosphates, dithiocarbamates and imidazoles and inorganic inhibitors in the form of oxides or hydroxides of aluminum, magnesium or silicon.
- a high temperature e.g. 300 C
- stabiliser such as heat-stable alkyl phenols, amines, aminophenols, dithiophosphates, dithiocarbamates and imidazoles and inorganic inhibitors in the form of oxides or hydroxides of aluminum, magnesium or silicon.
- EP 0078249 B1 is to the same general effect, and indicates that the additive may be a combination of a transition metal compound and an alkaline earth metal compound, as well as either such compound separately.
- G.B. Patent No. 1,413,323 describes a multi-component diesel fuel additive to avoid or reduce the formation of deposits on injector parts.
- the additive comprises, inter alia, an ester of oleic or naphthenic acid having an acid number below 200; a naphthenic acid ester of cresol; an alkoxyalkyl ester of an aliphatic carboxylic acid; an organometallic tricarbonyl cyclopentadiene compound such as cyclopentadienyl manganese tricarbonyl; an amide derivative of a polyolefin obtained by the reaction of a polyolefin substituted succinic acid or anhydride with a polyamine; a copolymer of ethylene and a vinyl (or hydrocarbyl-substituted vinyl) ester of a carboxylic acid wherein the copolymer has a number average molecular weight of more than 3000; a re-odoriser composed of a mixture of natural and synthetic alcohols, ketones
- compositions comprising the combination of a transition metal salt such as a manganese carboxylate, and an ashless hydrocarbon-soluble ashless dispersant.
- a transition metal salt such as a manganese carboxylate
- an ashless hydrocarbon-soluble ashless dispersant An optimum balance between beneficial and deleterious effects is said to be achieved in oils of lubricating viscosity and hydrocarbon fuels.
- additive compositions based on or including one or more fuel-soluble manganese carbonyl compounds and one or more fuel-soluble alkali and/or alkaline earth metal-containing detergents have been found in these laboratories to provide excellent improvements in the combustion characteristics of various hydrocarbonaceous fuels.
- additive combinations can cause fuel destabilisation -- i.e., the additives can cause the hydrocarbonaceous fuel with which they are blended to be less stable on exposure to air or oxygen at elevated temperatures than the fuel would be absent such additives.
- destabilisation of liquid hydrocarbonaceous fuels containing a combination of at least one fuel-soluble manganese carbonyl compound and at least one fuel-soluble alkali or alkaline earth metal-containing detergent is inhibited by inclusion in the fuel of at least one fuel-soluble metal deactivator of the chelation type, i.e., a metal deactivator capable of complexing dissolved metals or metal ions.
- this invention provides an additive composition for hydrocarbonaceous fuels.
- Such additive composition comprises:
- the additive compositions are thus composed of three different types of essential or indispensable ingredients, namely, components a), b), and c).
- this invention provides a fuel composition which comprises a major amount of a liquid hydrocarbonaceous fuel containing a minor combustion-improving amount of components a), b) and c) as just described.
- the additive compositions and fuel compositions are essentially halogen-free, that is, they contain no more than 10 ppm of halogen, if any.
- Preferred manganese carbonyl compounds -- component a) above -- are cyclopentadienyl manganese tricarbonyl compounds.
- the preferred component b) salts are the sodium, potassium, calcium and magnesium salts of sulphonic acids, of alkylphenols, of sulphurised alkylphenols, and of carboxylic acids, especially aromatic carboxylic acids.
- Preferred metal deactivators for use as component c) are fuel-soluble Schiff bases having one or more chelation centers of the formula
- the aromatic ring in the above formula can be further substituted or it can be unsubstituted, and if substituted can contain from 1 to 4 substituents (other than hydrogen atoms), which can be organic or inorganic of any types provided such substituent or plurality of substituents does not interfere with the ability of the metal deactivator to complex with dissolved metals or metal ions and does not otherwise render the metal deactivator unsuitable for use as, for example, by rendering it unstable, pyrophoric, highly toxic, explosive or fuel-insoluble. In other words, any such substituent(s) on the ring should be innocuous.
- a feature of this invention is the discovery that the metal deactivator can effectively inhibit fuel destabilisation even when present in the fuel in less than equimolar quantity with respect to either the manganese carbonyl compound(s) or the metal detergent(s) present therein.
- Another feature of this invention is the discovery that the metal deactivator can effectively inhibit fuel destabilisation while in the presence of still other additive components, such as ashless dispersants, amine stabilisers, and demulsifying agents.
- compositions for use in heating gas oils and similar burner fuels preferably contain, in addition to components a), b) and c) above, one or more of the following:
- Compositions for use in road diesel fuels and similar middle distillate fuels preferably contain, in addition to components a), b) and c) above, component d), namely, at least one ashless dispersant and/or component e), namely, at least one fuel-soluble demulsifying agent.
- fuel-soluble means that the compound or component under discussion has sufficient solubility at ordinary ambient temperature in the hydrocarbonaceous fuel in which it is to be used to provide a homogeneous solution containing the compound or component in at least the lowest concentration of the concentration ranges specified herein for such compound or component.
- the manganese compounds -- component a) -- of the compositions of this invention are characterised by being fuel soluble and by having at least one carbonyl group bonded to a manganese atom.
- the most desirable general type of manganese carbonyl compounds utilised in accordance with this invention comprise organomanganese polycarbonyl compounds.
- organomanganese polycarbonyl compounds For best results, use should be made of a cyclopentadienyl manganese tricarbonyl compound of the type described in U. S. Pat. Nos. 2,818,417 and 3,127,351.
- cyclopentadienyl manganese tricarbonyl methylcyclopentadienyl manganese tricarbonyl, ethylcyclopentadienyl manganese tricarbonyl, dimethyl- cyclopentadienyl manganese tricarbonyl, trimethylcyclopentadienyl manganese tricarbonyl, propylcyclopen- tadienyl manganese tricarbonyl, isopropylcyclopentadienyl manganese tricarbonyl, butylcyclopentadienyl manganese tricarbonyl, pentylcyclopentadienyl manganese tricarbonyl, hexylcyclopentadienyl manganese tricarbonyl, ethylmethylcyclopentadienyl manganese tricarbonyl, dimethyloctylcyclopentadienyl manganese tricarbonyl, dodecyl
- a preferred organomanganese compound is cyclopentadienyl manganese tricarbonyl. Particularly preferred for use in the practise of this invention is methylcyclopentadienyl manganese tricarbonyl.
- organomanganese compounds which may be employed include the non-ionic diamine manganese tricarbonyl halide compounds such as bromo manganese dianiline tricarbonyl and bromo manganese dipyridine tricarbonyl, described in U. S. Pat. No. 2,902,489; the acyl manganese tricarbonyls such as methylacetyl cyclopentadienyl manganese tricarbonyl and benzoyl methyl cyclopentadienyl manganese tricarbonyl, described in U. S. Pat. No.
- cyclopentadienyl manganese dicarbonyl compounds of the formula RMn(CO) 2 L where R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms, and L is a ligand, such as an olefin, an amine, a phosphine, S0 2 , tetrahydrofuran, or the like.
- R is a substituted or unsubstituted cyclopentadienyl group having 5 to 18 carbon atoms
- L is a ligand, such as an olefin, an amine, a phosphine, S0 2 , tetrahydrofuran, or the like.
- Such compounds are referred to, for example in, Herberhold, M., Metal 1T -Complexes, Vol. II, Amsterdam, Elsevier, 1967 or Giordano, P. J. and Weighton, M.S., Inorg
- Metal-containing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with one or more of the following acidic substances (or mixtures thereof): (1) sulphonic acids, (2) carboxylic acids, (3) salicylic acids, (4) alkylphenols, (5) sulphurised alkylphenols, (6) organic phosphorus acids characterised by at least one direct carbon-to-phosphorus linkage.
- Such organic phosphorus acids include those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorising agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulphide, phosphorus trichloride and sulphur, white phosphorus and a sulphur halide, or phosphorothioic chloride.
- a phosphorising agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulphide, phosphorus trichloride and sulphur, white phosphorus and a sulphur halide, or phosphorothioic chloride.
- phosphorising agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulphide, phosphorus trichloride
- basic salt is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical.
- the commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralising agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulphide at a temperature of about 50 °C, and filtering the resulting mass.
- a “promoter” in the neutralisation step to aid the incorporation of a large excess of metal likewise is known.
- Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulphurised alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine.
- a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralising agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60 ° -200 ° C.
- suitable metal-containing detergents include, but are not limited to, such substances as lithium phenates, sodium phenates, potassium phenates, calcium phenates, magnesium phenates, sulphurised lithium phenates, sulphurised sodium phenates, sulphurised potassium phenates, sulphurised calcium phenates, and sulphurised magnesium phenates wherein each aromatic group has one or more aliphatic groups to impart hydrocarbon solubility; the basic salts of any of the foregoing phenols or sulphurised phenols (often referred to as "overbased" phenates or "overbased sulphurised phenates”); lithium sulphonates, sodium sulphonates, potassium sulphonates, calcium sulphonates, and magnesium sulphonates wherein each sulphonic acid moiety is attached to an aromatic nucleus which in turn usually contains one or more aliphatic substituents to impart hydrocarbon solubility; the basic salts of any of the foregoing
- salts of two or more different alkali and/or alkaline earth metals can be used.
- salts of mixtures of two or more different acids or two or more different types of acids e.g., one or more calcium phenates with one or more calcium sulphonates
- rubidium, cesium and strontium salts are feasible, their expense renders them impractical for most uses.
- barium salts are effective, the status of barium as a heavy metal under a toxicological cloud renders barium salts less preferred for present-day usage.
- component c) -- the third indispensable component of the compositions of this invention -- is a metal deactivator of the chelator type, i.e., one or more substances which have the capability of reacting or complexing with dissolved metal and/or metal ions.
- the chelator type of metal deactivators include 8-hydroxyquinoline, ethylene diamine tetracarboxylic acid, ;8-diketones such as acetylacetone, (3-ketoesters such as octyl acetoacetate, and the like.
- the preferred metal deactivators generally regarded as chelators are Schiff bases, such as N,N'-disalicylidene-1,2-ethanediamine, N,N'-disalicylidene-1,2-propanediamine, N,N'-disalicylidene-1,3-propanediamine, N,N'- disalicylidene-1,2-cyclohexanediamine, N,N"-disalicylidene-N'-methyl-dipropylenetriamine, 3'-ethoxy-5,2',6'-trimethyl-N,N'-disalicylidene-biphenyl-2,4'-diyldiamine, 5'-ethoxy-3,5,2'-trimethyl-N,N'-disalicylidene- biphenyl-2,4'-diyldiamine, and analogous compounds in which one or more of the salicylidene groups are substituted by innocuous groups such as alkyl, alk
- metal deactivators are available for use as component c) in the practise of this invention.
- the most preferred metal deactivators of this type are N,N'-disalicylidene-1,2-alkanediamines and N,N'-disalicylidene-1,2-cycloalkanediamines, especially N,N'-disalicylidene-1,2-propanediamine. Mixtures of metal deactivators can be used.
- additional components d), e) and f) which may be utilised in the compositions of this invention.
- these additional components do not materially interfere with the enhanced fuel stability realised by combining component c) with components a) and b).
- component c) with components a) and b).
- Ashless dispersants which make up component d
- Ashless dispersants are described in numerous patent specifications, mainly as additives for use in lubricant compositions, but their use in hydrocarbon fuels has also been described.
- Ashless dispersants leave little or no metal-containing residue on combustion. They generally contain only carbon, hydrogen, oxygen and in most cases nitrogen, but sometimes contain in addition other non-metallic elements such as phosphorus, sulphur or boron.
- the preferred ashless dispersant is an alkenyl succinimide of an amine having at least one primary amino group capable of forming an imide group.
- alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with an amine containing at least one primary amino group.
- the alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to about 180 *- 220 * C.
- the olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, isobutene and the like.
- the more preferred source of alkenyl group is from polyisobutene having a molecular weight up to 10,000 or higher.
- the alkenyl group is a polyisobutene group having a molecular weight of about 500-5,000, preferably about 900-2,000, and especially about 900-1,200.
- Amines which may be employed in forming the ashless dispersant include any that have at least one primary amino group which can react to form an imide group.
- a few representative examples are: methylamine, 2-ethylhexylamine, n-dodecylamine, stearylamine, N,N-dimethylpropanediamine, N-(3-aminopropyl)morpholine, N-dodecylpropanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol- ethylenediamine and the like.
- the preferred amines are the alkylene polyamines such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, and tetra-(1,2-propylene)pentamine.
- the most preferred amines are the ethylene polyamines which can be depicted by the formula wherein n is an integer from one to about ten. These include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like, including mixtures thereof in which case n is the average value of the mixture. These ethylene polyamines have a primary amine group at each end so can form mono-alkenylsuccinimides and bis-alkenylsuccinimides.
- ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis(piperazinyl)ethane, and like compounds.
- the preferred commercial mixtures have approximate overall compositions falling in the range corresponding to diethylene triamine to tetraethylene pentamine, mixtures generally corresponding in overall makeup to tetraethylene pentamine being most preferred.
- especially preferred ashless dispersants for use in the present invention are the products of reaction of a polyethylene polyamine, e.g. triethylene tetramine or tetraethylene pentamine with a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, preferably polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 900 to 2,000 and especially 900 to 1,200, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures of two or more such substances.
- a polyethylene polyamine e.g. triethylene tetramine or tetraethylene pentamine
- a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, preferably polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 900 to 2,000 and
- alkenyl succinic acid esters and diesters of alcohols containing 1-20 carbon atoms and 1-6 hydroxyl groups Representative examples are described in U.S. Pat. Nos. 3,331,776; 3,381,022; and 3,522,179.
- the alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above including the same preferred and most preferred subgenus, e.g., polyisobutenyl succinic acids wherein the polyisobutenyl group has a number average molecular weight of 500 to 5,000, preferably 900-2,000, especially 900 to 1,200.
- Alcohols useful in preparing the esters include methanol, ethanol, isobutanol, octadecanol, eicosanol, ethylene glycol, diethylene glycol, tetraethylene glycol, diethylene glycol monoethylether, propylene glycol, tripropylene glycol, glycerol, sorbitol, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, 1,1,1-trimethylol butane, pentaerythritol, dipentaerythritol, and the like.
- the succinic esters are readily made by merely heating a mixture of alkenyl succinic acid, anhydrides or lower alkyl (e.g., C 1 -C 4 ) ester with the alcohol while distilling out water or lower alkanol. In the case of acid-esters less alcohol is used. In fact, acid-esters made from alkenyl succinic anhydrides do not evolve water. In another method the alkenyl succinic acid or anhydrides can be merely reacted with an appropriate alkylene oxide such as ethylene oxide, propylene oxide, and the like, including mixtures thereof.
- an appropriate alkylene oxide such as ethylene oxide, propylene oxide, and the like, including mixtures thereof.
- the ashless dispersant is an alkenyl succinic ester-amide mixture.
- alkenyl succinic ester-amide mixture may be made by heating the above-described alkenyl succinic acids, anhydrides or lower alkyl esters with an alcohol and an amine either sequentially or in a mixture.
- the alcohols and amines described above are also useful in this embodiment.
- amino alcohols can be used alone or with the alcohol and/or amine to form the ester-amide mixtures.
- the amino alcohol can contain 1-20 carbon atoms, 1-6 hydroxy groups and 1-4 amine nitrogen atoms. Examples are ethanolamine, diethanolamine, N-ethanol-diethylene triamine, and trimethylol aminomethane.
- ester-amide mixtures are described in U.S. Pat. Nos. 3,184,474; 3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,991,098; 4,071,548; and 4,173,540.
- Such ashless dispersants containing alkenyl succinic residues may, and as is well known, be post- reacted with boron compounds, phosphorus derivatives and/or carboxylic acid acylating agents, e.g. maleic anhydride.
- Another useful class of ashless dispersants includes the Mannich condensates of hydrocarbyl-substituted phenols, formaldehyde or formaldehyde precursors (e.g. paraformaldehyde) and an amine having at least one primary amine group and containing 1-10 amine groups and 1-20 carbon atoms.
- Mannich condensates useful in this invention are described in U.S. Pat. Nos.
- Mannich condensates are those made by condensing a polyisobutenyl phenol wherein the polyisobutyl group has an average molecular weight of about 800-3,000 with formaldehyde or a formaldehyde precursor and an ethylene polyamine having the formula:
- a further type of ashless dispersants which can be used comprises interpolymers of oil-solubilising monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly(oxyethylene)-substituted acrylates.
- polar substituents e.g., aminoalkyl acrylates or acrylamides and poly(oxyethylene)-substituted acrylates.
- Another class of ashless dispersants which can advantageously be used in the fuel compositions of this invention are the imidazoline dispersants which can be represented by the formula: wherein R 1 represents a hydrocarbon group having 1 to 30 carbon atoms, e.g. an alkyl or alkenyl group having 7 to 22 carbon atoms, and R 2 represents a hydrogen atoms or a hydrocarbon radical of 1 to 22 carbon atoms, or an aminoalkyl, acylaminoalkyl or hydroxyalkyl radical having 2 to 50 carbon atoms.
- R 1 represents a hydrocarbon group having 1 to 30 carbon atoms, e.g. an alkyl or alkenyl group having 7 to 22 carbon atoms
- R 2 represents a hydrogen atoms or a hydrocarbon radical of 1 to 22 carbon atoms, or an aminoalkyl, acylaminoalkyl or hydroxyalkyl radical having 2 to 50 carbon atoms.
- Such long-chain alkyl (or long-chain alkenyl) imidazoline compounds may be made by reaction of a corresponding long-chain fatty acid (of formula Ri-COOH), for example oleic acid, with an appropriate polyamine.
- the imidazoline formed is then ordinarily called, for example, oleylimidazoline where the radical R 1 represents the oleyl residue of oleic acid.
- Other suitable alkyl substituents in the 2- position of these imidazolines include undecyl, heptadecyl, lauryl and erucyl.
- Suitable N-substituents of the imidazolines i.e.
- radicals R 2 include hydrocarbyl groups, hydroxyalkyl groups, aminoalkyl groups, and acylaminoalkyl groups. Examples of these various groups include methyl, butyl, decyl, cyclohexyl, phenyl, benzyl, tolyl, hydroxyethyl, aminoethyl, oleylaminoethyl and stearylaminoethyl.
- polyamines examples include N-oleyl-1,3-propanediamine, N-stearyl-1,3-propanediamine, N-oleyl-1,3-butanediamine, N-oleyl-2-methyl-1,3-propanediamine, N-oleyl-1,3-pentanediamine, N-oleyl-2-ethyl-1,3-propanediamine, N-stearyl-1,3-butanediamine, N-stearyl-2-methyl-1,3-propanediamine, N-stearyl-1,3-pentanediamine, N-stearyl-2-ethyl-1,3-propanediamine, N-oleyl-dipropylenetriamine and N-stearyl- dipropylenetriamine.
- Such linear N-alkylpolyamines are condensed with, e.g., a succinic, maleic, phthalic or hexahydrophthalic acid anhydride which may be substituted by one or more radicals of up to 5 carbon atoms each.
- Another class of ashless dispersant which can be incorporated in the compositions of the present invention are the products of reaction of an ethoxylated amine made by reaction of ammonia with ethylene oxide with a carboxylic acid of 8 to 30 carbon atoms.
- the ethoxylated amine may be, for example, mono-, di- or tri-ethanolamine or a polyethoxylated derivative thereof, and the carboxylic acid may be, for example, a straight or branched chain fatty acid of 10 to 22 carbon atoms, a naphthenic acid, a resinic acid or an alkyl aryl carboxylic acid.
- Still another type of ashless dispersants which can be used in the practise of this invention are the a-olefin-maleimide copolymers such as are described in U.S. Pat. No. 3,909,215.
- Such copolymers are alternating copolymers of N-substituted maleimides and aliphatic a-olefins of from 8 to 30 carbon atoms.
- the copolymers may have an average of 4 to 20 maleimide groups per molecule.
- the substituents on the nitrogen of the maleimide may be the same or different and are organic radicals composed essentially of carbon, hydrogen and nitrogen having a total of 3 to 60 carbon atoms.
- a commercially available material which is highly suitable for use in this invention is Chevron OFA 425B, and this material is believed to be or comprise an a-olefin maleimide copolymer of the type described in U.S. Pat. No. 3,909,215. Whatever its composition, it works quite well.
- ashless dispersants which contain little, if any, halogen atoms such as chlorine atoms.
- the additive composition contains no detectable amount of halogen.
- Typical halogen (chlorine)-free ashless dispersants suitable for use in the compositions of this invention include, in addition to various types described hereinabove, those described in the following recently- published applications: WO 9003359 and EP 365288.
- Demulsifying agents Any of a variety of demulsifying agents can be used in the fuel and fuel additive compositions of this invention.
- the demulsifying agent improves the water tolerance level of the fuel compositions by minimizing or preventing excessive emulsion formation.
- demulsifiers which may be employed include poly(alkylphenol) formaldehyde condensates and the polyalkylenoxy modified reaction products thereof. These compounds are prepared by reacting an alkylphenol with formaldehyde and thereafter reacting the reaction product of the above with a C 2 to C 6 alkylene oxide such as ethylene oxide and propylene oxide.
- the demulsifiers have a generalized structural formula wherein U is an alkylene of 2 to 6 carbons; y is an integer averaging between 4 and 10; x is an integer averaging between 4 and 10; and R 5 is an alkyl having from 4 to 15 carbon atoms.
- Preferred demulsifiers described by the above formula are polyethyleneoxy modified methylene bridged poly(alkylphenol) polymers having a polyethyleneoxy chain of 8 to 20 carbons and preferably from 10 to 16 carbons and at least about 75 number percent of the polyethyleneoxy chains being within the range specified.
- the methylene bridged poly(alkylphenol) portion of the polymer has from 4 to 10 and preferably from 5 to 8 repeating methylene bridged alkylphenol units with 4 to 15 and preferably 6 to 12 carbons in the alkyl group.
- the alkyl groups are a mixture of alkyls having between 4 and 12 carbon atoms.
- Illustrative alkylphenols include p-isobutylphenol, p-diisobutylphenol, p-hexylphenol, p-heptylphenol, p-octylphenol, p-tripropylenephenol, and p-dipropylenephenol, etc.
- demulsifier component is an ammonia-neutralised sulphonated alkylphenol.
- R 1 is a hydrocarbyl group having from 4 to 15 carbon atoms, preferably from 6 to 12.
- These compounds are prepared by sulphonating an alkylated phenol and thereafter neutralising the sulphonated product with ammonia.
- demulsifier is an oxyalkylated glycol.
- These compounds are prepared by reacting a polyhydroxy alcohol such as ethylene glycol, trimethylene glycol, etc., with ethylene or propylene oxide.
- ethylene glycol trimethylene glycol, etc.
- propylene oxide ethylene or propylene oxide.
- Many of the compounds are commercially available from BASF-Wyandotte Chemical Company under the PLURONIC trademark. They are polyethers terminated by hydroxy groups and produced by the block copolymerisation of ethylene oxide and propylene oxide.
- the ethylene oxide blocks act as the hydrophiles and the propylene oxide blocks as the hydrophobes. They are available in a wide range of molecular weights and with varying ratios of ethylene oxide to propylene oxide.
- demulsifiers comprises a mixture of alkylaryl sulphonates, polyoxyalkylene glycols and oxyalkylated alkylphenolic resins.
- Such products are supplied by Petrolite Corporation under the TOLAD trademark.
- One such propriety product, identified as TOLAD 286K, is understood to be a mixture of these components dissolved in a solvent composed of alkyl benzenes. This product has been found efficacious for use in the compositions of this invention.
- a related product, TOLAD 286, is also suitable. In this case the product apparently contains the same kind of active ingredients dissolved in a solvent composed of heavy aromatic naphtha and isopropanol.
- other known demulsifiers can be used.
- Aliphatic or cycloaliphatic amine When it is desired to include one or more amines in the compositions of this invention, any of a wide variety of suitable amines can be used. This component contributes stability to the systems in which it is employed. Typically a monoamine is employed although polyamines can be used, if desired. Among the vast array of suitable amines are included the amines referred to in U.S. Pat. No. 3,909,215 such as tertiary alkyl primary amines including Primene 81 R and the like, and amines referred to in EP 188,042, namely alkyldimethylamines in which the alkyl group has 8 to 14 carbon atoms or mixtures thereof.
- mixed alkyl-cycloalkyl amines such as N-cyclohexyl-N-butyl amine, N-methylcyclohexyl-N-octyl amine, etc., as well as di- and tricycloalkyl amines such as N,N-dicyclohexyl amine, N,N-di-(ethylcyclohexyl)amine, N,N,N-tricyclohexyl amine, and the like.
- Preferred amines include N-cycloalkyl-N,N-dialkyl amines and N-cycloalkenyl-N,N-dialkylamines such as N-cyclohexyl-N,N-diethyl amine, N-cyclohexyl-N,N-dibutyl amine, N-cycloheptyl-N,N-dimethyl amine, N-cyclooctyl-N,N-dilauryl amine, N-cyclohexenyl-N,N-dipropyl amine, and like compounds. Particularly preferred is N-cyclohexyl-N,N-dimethyl amine. Mixtures of various amines, such as those referred to above, are also suitable for use in accordance with this invention.
- Hydrocarbonaceous fuels In principle, the advantages of this invention may be achieved in any liquid hydrocarbonaceous fuel derived from petroleum, coal, shale and/or tar sands. In most instances, at least under present circumstances, the base fuels will be derived primarily, if not exclusively, from petroleum.
- the invention is thus applicable to such fuels as kerosene, jet fuel, aviation fuel, diesel fuel, home heating oil, light cycle oil, heavy cycle oil, light gas oil, heavy gas oil, bunker fuels, residual fuel oils, ultra heavy fuel oils, and in general, any liquid (or flowable) hydrocarbonaceous product suitable for combustion either in an engine (e.g., diesel fuel, gas turbine fuels, etc.) or in a burner apparatus (e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.).
- an engine e.g., diesel fuel, gas turbine fuels, etc.
- a burner apparatus e.g., gas oils, inland heavy fuel oil, residual fuel oils, visbreaker fuel oils, home heating oils, etc.
- suitable fuels may include liquid fuels derived from biomass, such as vegetable oils (e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.); or refuse-derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
- vegetable oils e.g., rapeseed oil, jojoba oil, cottonseed oil, etc.
- refuse-derived liquid fuels such as fuels derived from municipal and/or industrial wastes; or waste oils and/or liquid waste biomass and its derivatives; or mixtures of any of the foregoing substances.
- the additive compositions comprising components a), b), c) and at least one of components d), e) and f) --preferably two of components d), e) and f) and most preferably all three of components d), e) and f) -are especially useful in heating gas oils and like burner fuels and fuel oils for agricultural and industrial engines.
- Typical specifications for such fuel oils can be found, for example, in BS 2869 : Part 2 : 1988 of the British Standards Institution.
- a vast number of such specifications exist from country to country.
- the components of the additive compositions are employed in the fuels in minor amounts sufficient to improve the combustion characteristics and properties of the base hydrocarbonaceous fuel in which they are employed.
- the metal deactivator, component c) is employed in a minor amount sufficient to inhibit fuel destabilisation in fuels containing components a) and b).
- the amounts will thus vary in accordance with such factors as base fuel type and service conditions for which the finished fuel is intended.
- concentrations (ppm) of the components (active ingredients) in the base fuels are illustrative:
- the individual components a), b), and c), and also d), e), and/or f) (if used), can be separately blended into the fuel or can be blended therein in various subcombinations, if desired.
- the particular sequence of such blending steps is not critical.
- such components can be blended in the form of a solution in a diluent. It is preferable, however, to blend the components used in the form of an additive concentrate of this invention, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
- the additive concentrates of this invention will contain components a), b), and c), and optionally, but preferably, one or more of components d), e), and f) in amounts proportioned to yield fuel blends consistent with the concentrations tabulated above.
- the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate.
- concentrates containing up to 90% by weight of one or more diluents or solvents are frequently used.
- the additive compositions and fuel compositions of this invention can also contain antioxidant, e.g., one or more phenolic antioxidants, aromatic amine antioxidants, sulphurised phenolic antioxidants, and organic phosphites, among others.
- antioxidant e.g., one or more phenolic antioxidants, aromatic amine antioxidants, sulphurised phenolic antioxidants, and organic phosphites, among others.
- Examples include 2,6-di-tert-butylphenol, liquid mixtures of tertiary butylated phenols, 2,6-di-tert-butyl-4-methylphenol, 4,4'-methy!enebis(2,6-di-tert-buty!pheno!), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), mixed methylene- bridged polyalkyl phenols, 4,4'-thiobis(2-methyl-6-tert-butylphenol), N,N'-di-sec-butyl-p-phenylenediamine, 4-isopropylaminodiphenyl amine, phenyl-a-naphthyl amine, and phenyl-Q-naphthylamine.
- Corrosion inhibitors comprise another type of optional additive for use in this invention.
- dimer and trimer acids such as are produced from tall oil fatty acids, oleic acid, linoleic acid, or the like. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humco Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals.
- alkenyl succinic acid and alkenyl succinic anhydride corrosion inhibitors such as, for example, tetrapropenylsuccinic acid, tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid, tetradecenylsuccinic anhydride, hexadecenylsuccinic acid, hexadecenylsuccinic anhydride, and the like.
- half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols.
- Preferred materials are the aminosuccinic acids or derivatives thereof represented by the formula: wherein each of R 1 , R 2 , R 5 , R 6 and R 7 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of R 3 and R 4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 when in the form of a hydrocarbyl group, can be, for example, alkyl, cycloalkyl or aromatic containing groups.
- R 1 and R 5 are the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms.
- R 1 and R 5 are saturated hydrocarbon radicals containing 3-6 carbon atoms.
- R 2 , either R 3 or R 4 , R 6 and R 7 when in the form of hydrocarbyl groups, are preferably the same or different straight-chain or branched-chain saturated hydrocarbon radicals.
- a dialkyl ester of an aminosuccinic acid is used in which R 1 and R 5 are the same or different alkyl groups containing 3-6 carbon atoms, R 2 is a hydrogen atom, and either R 3 or R 4 is an alkyl group containing 15-20 carbon atoms or an acyl group which is derived from a saturated or unsaturated carboxylic acid containing 2-10 carbon atoms.
- R 1 and R 5 are isobutyl
- R 2 is a hydrogen atom
- R 3 is octadecyl and/or octadecenyl
- R 4 is 3-carboxy-1-oxo-2-propenyl.
- R 6 and R 7 are most preferably hydrogen atoms.
- the heavier fuels of this invention may contain cold flow improvers and pour-point depressants, e.g., olefin/vinyl acetate copolymers such as ethylene/vinyl acetate copolymers and polymethacrylates.
- Antifoam agents such as silicones; metal deactivators of the passivator type, e.g., the thiadiazoles such as HITEC@ 314 additive (Ethyl Petroleum Additives, Ltd.; Ethyl Petroleum Additives, Inc.); and dyes can also be used in the compositions of this invention.
- the diesel fuels may contain cetane improvers such as peroxy compounds and organic nitrates (e.g., amyl nitrates, hexyl nitrates, heptyl nitrates, octyl nitrates, and other alkyl nitrates having about 4 to about 10 carbon atoms including mixtures thereof).
- cetane improvers such as peroxy compounds and organic nitrates (e.g., amyl nitrates, hexyl nitrates, heptyl nitrates, octyl nitrates, and other alkyl nitrates having about 4 to about 10 carbon atoms including mixtures thereof).
- alkyl nitrates are cyclohexyl nitrate, methoxypropyl nitrate, mixed nitrate esters made by nitration of fusel oil, 2-ethylhexyl nitrate, n-octyl nitrate, n-decyl nitrate, etc.
- Typical peroxy compounds include acetyl peroxide, benzoyl peroxide, tert-butylperoxyacetate, and cumene hydroperoxide.
- An additive composition is formed by blending together the following components in the amounts specified:
- This composition is well adapted for use in heating gas oil, for example at treat rates of 250 to 37,000 ppm, typically 500 ppm.
- An additive composition is formed by blending together the following components in the amounts specified:
- This composition is well adapted for use in heating gas oil, for example at treat rates of 250 to 37,000 ppm, typically 500 ppm.
- An additive composition is formed by blending together the following components in the amounts specified:
- This composition is well adapted for use in heating gas oil, for example at treat rates of 250 to 37,000 ppm, typically 500 ppm.
- An additive composition is formed by blending together the following components in the amounts specified:
- This composition is well adapted for use in heating gas oil, for example at treat rates of 250 to 37,000 ppm, typically 500 ppm.
- An additive composition of this invention is formed using the following:
- This composition is useful, for example at treat rates of 250 to 37,000 ppm, typically 500 ppm, in heating gas oils.
- this additive concentrate When used, for example at a concentration in the range of 200 to 26,500 ppm, typically 400 ppm, this additive concentrate is especially adapted for improving combustion of road diesel fuels.
- An additive concentrate is formed using the following components:
- Examples 9 and 10 are repeated substituting in one case overbased potassium sulphonate and in another case overbased calcium phenate for the sulphonates of Examples 9 and 10.
- compositions of Examples 1 through 9 and 12 are formed with the exception that the methylcyclopentadienyl manganese tricarbonyl is replaced in one case by an equivalent amount of cyclopentadienyl manganese tricarbonyl, in another case by an equivalent amount of cyclopentadienyl manganese dicarboxyl triphenylphosphine, in a third case by an equivalent amount of indenyl manganese tricarbonyl, in a fourth case by an equivalent amount of dimanganese decacarbonyl, and in still another case by an equivalent amount of a mixture composed of 90% methylcyclopentadienyl manganese tricarbonyl and 10% cyclopentadienyl manganese tricarbonyl.
- compositions of Examples 4 and 7 are blended at concentrations of 300, 500 and 1,000 ppm in a heating gas oil having a specific gravity at 15 ° C (DIN 51 757) of 0.845 g/mL, a kinematic viscosity at 20 ° C (DIN 51 562) of 5.3 mm 2 per second, a pour point (DIN ISO 3016) of -9 ° C, a sulphur content (DIN 51 400) of 0.19%, and a distillation profile (DIN 51 751) of 27 volume % boiling to 250 ° C and 92 volume % boiling to 350 C.
- DIN 51 757 a heating gas oil having a specific gravity at 15 ° C (DIN 51 757) of 0.845 g/mL, a kinematic viscosity at 20 ° C (DIN 51 562) of 5.3 mm 2 per second, a pour point (DIN ISO 3016) of -9 ° C, a sulphur content (DIN 51 400) of
- Example 14 is repeated except that the same amounts of the respective components of the respective compositions of Examples 4 and 7 are blended individually or in sub-combinations into the gas oil.
- Example 8 The composition of Example 8 is blended at concentrations of 300, 500, 1,000 and 1,500 ppm in a diesel fuel satisfying the requirements of DIN 51 601-DK (February 1986).
- Example 16 is repeated except that the same amounts of the respective components of the composition of Example 8 are blended individually or in sub-combinations into the diesel fuel.
- Examples 16 and 17 are repeated using commercially available diesel fuels suitable for use as railway diesel fuel, tractor diesel fuel, off-road diesel fuel and inland waterways fuel.
- Examples 14 and 15 are repeated using as the fuels commercially-available heavy fuel oils and residual oils (e.g., industrial and refinery fuel oils) such as inland heavy fuel oils, and also hydrocarbonaceous marine fuels.
- the additive treat levels in these fuels are 500, 800 and 1,500 ppm.
- Standard CFR engine tests (ASTM D613) were conducted using two different diesel fuels having cetane values of 52.7 (Fuel A) and 52.5 (Fuel B), respectively.
- Fuel B only a slight loss in cetane value (from 52.5 to 51.6) occurred by addition of 500 ppm of the composition of Example 4.
- the fuels of this invention generally possess enhanced combustion properties (e.g., less smoke, lower soot acidity) and better thermal stability than the corresponding untreated fuels.
- use of the fuels of this invention results in the formation of reduced amounts of sludge deposits on critical engine or burner parts or surfaces. Further, such fuels tend to emit smaller amounts of noxious emissions than the corresponding untreated base fuels.
- this invention enables the provision of fuel compositions having enhanced demulsification properties and reduced corrosion tendencies with minimal interference with other desirable fuel properties.
- the additive compositions of this invention can result in decreased fuel consumption in diesel engines.
- the above data indicate that all fuels do not necessarily respond to the same extent to treatment with the additive systems of this invention. Nonetheless, as a general proposition, the fuels of this invention do have significantly improved properties.
- compositions preferably contain one or more of components d), e) and f) as described hereinabove.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES90310323T ES2048439T3 (es) | 1990-09-20 | 1990-09-20 | Composiciones combustibles hidrocarbonadas y aditivos para ellas. |
EP90310323A EP0476197B1 (de) | 1990-09-20 | 1990-09-20 | Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu |
DE90310323T DE69006029T2 (de) | 1990-09-20 | 1990-09-20 | Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu. |
CA002051451A CA2051451C (en) | 1990-09-20 | 1991-09-16 | Hydrocarbonaceous fuel compositions and additives therefor |
JP3265495A JP2965764B2 (ja) | 1990-09-20 | 1991-09-18 | 炭化水素性燃料およびその添加剤 |
AU84653/91A AU634422B2 (en) | 1990-09-20 | 1991-09-20 | Hydrocarbonaceous fuel compositions and additives therefor |
Applications Claiming Priority (1)
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EP90310323A EP0476197B1 (de) | 1990-09-20 | 1990-09-20 | Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu |
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EP0476197A1 true EP0476197A1 (de) | 1992-03-25 |
EP0476197B1 EP0476197B1 (de) | 1994-01-12 |
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EP90310323A Expired - Lifetime EP0476197B1 (de) | 1990-09-20 | 1990-09-20 | Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu |
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Country | Link |
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EP (1) | EP0476197B1 (de) |
JP (1) | JP2965764B2 (de) |
AU (1) | AU634422B2 (de) |
CA (1) | CA2051451C (de) |
DE (1) | DE69006029T2 (de) |
ES (1) | ES2048439T3 (de) |
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EP0626442A1 (de) * | 1993-05-24 | 1994-11-30 | The Lubrizol Corporation | Mit einem Stockpunkterniedrigtem behandelte Fettsäureester, als biologisch abbaubare Verbrennungsmotorkraftstoffe |
EP0629233A1 (de) * | 1992-12-28 | 1994-12-21 | Chevron Chemical Company | Brennstoffzusatzzusammensetzungen, die aliphatische amine und polyalkylhydroxyaromate enthalten |
GB2285057A (en) * | 1993-12-23 | 1995-06-28 | Ethyl Petroleum Additives Ltd | Evaporative burner fuels and additives therefor |
EP0678568A1 (de) * | 1994-04-19 | 1995-10-25 | Betz Europe, Inc. | Verfahren und Zusammensetzungen zur Strahltriebwerksverschmutzungsniederschlagsbildungverminderung |
US5551957A (en) * | 1992-05-06 | 1996-09-03 | Ethyl Corporation | Compostions for control of induction system deposits |
WO1996040844A1 (en) * | 1995-06-07 | 1996-12-19 | Orr William C | Vapor phase combustion method and compositions ii |
US5596130A (en) * | 1994-04-19 | 1997-01-21 | Betz Laboratories, Inc. | Methods and compositions for reducing fouling deposit formation in jet engines |
US5792735A (en) * | 1994-01-11 | 1998-08-11 | Bp Chemicals (Additives) Limited | Lubricating oil compositions |
US5928392A (en) * | 1996-05-14 | 1999-07-27 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
EP1050573A3 (de) * | 1994-12-13 | 2001-01-03 | Infineum USA L.P. | Brennölzusammensetzungen |
FR2839315A1 (fr) * | 2002-05-03 | 2003-11-07 | Totalfinaelf France | Additif pour ameliorer la stabilite thermique de compositions d'hydrocarbures |
EP1496100A1 (de) * | 2003-07-08 | 2005-01-12 | Ethyl Petroleum Additives, Inc. | Destillattreibstoffezusammensetzungen zur Verbesserung der Verbrennung und der Motorsauberkeit. |
WO2005003265A1 (en) * | 2003-06-25 | 2005-01-13 | The Lubrizol Corporation | Gel additives for fuel that reduce soot and/or emissions from engines |
WO2005087901A2 (en) * | 2004-03-09 | 2005-09-22 | Innospec Limited | Fuel additive composition having antiknock properties |
EP1854867A1 (de) | 2006-05-12 | 2007-11-14 | Repsol Ypf S.A. | Neue stabilisierte Kraftstoffzusammensetzung |
EP2147966A1 (de) * | 2008-07-25 | 2010-01-27 | Total Raffinage Marketing | Zusatzstoff für flüssigen Brennstoff, der ihn enthaltende flüssige Brennstoff und seine Anwendung für Energieerzeugungsgeräte und/oder Heizgeräte und/oder Kochgeräte |
WO2012023872A2 (en) | 2010-02-10 | 2012-02-23 | Marine Resources Exploration International B.V. | Synergistic compositions of anti-explosive additives for gasolines |
WO2020117520A1 (en) * | 2018-12-07 | 2020-06-11 | Exxonmobil Research And Engineering Company | Fuel high temperature antioxidant additive |
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DE20212106U1 (de) * | 2002-08-06 | 2003-03-06 | Grafenhorst, Heinrich, 28215 Bremen | Gasturbinenantrieb, insbesondere für Propeller-Flugzeuge |
US7332001B2 (en) | 2003-10-02 | 2008-02-19 | Afton Chemical Corporation | Method of enhancing the operation of diesel fuel combustion systems |
DE102005045134B4 (de) * | 2005-09-22 | 2010-12-30 | Clariant Produkte (Deutschland) Gmbh | Alkylphenol-Aldehydharze, diese enthaltende Zusammensetzungen zu Verbesserung der Kältefließfähigkeit und Schmierfähigkeit von Brennstoffölen sowie deren Verwendung |
US8163042B2 (en) * | 2006-11-01 | 2012-04-24 | Bharat Petroleum Corporation Limited | Hydrocarbon fuel compositions |
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- 1990-09-20 EP EP90310323A patent/EP0476197B1/de not_active Expired - Lifetime
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- 1991-09-16 CA CA002051451A patent/CA2051451C/en not_active Expired - Fee Related
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- 1991-09-20 AU AU84653/91A patent/AU634422B2/en not_active Ceased
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Cited By (31)
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US5551957A (en) * | 1992-05-06 | 1996-09-03 | Ethyl Corporation | Compostions for control of induction system deposits |
US5743923A (en) * | 1992-10-26 | 1998-04-28 | Exxon Chemical Patents Inc. | Oil additives and compositions |
WO1994010267A1 (en) * | 1992-10-26 | 1994-05-11 | Exxon Chemical Patents Inc. | Oil additives and compositions |
EP0629233A1 (de) * | 1992-12-28 | 1994-12-21 | Chevron Chemical Company | Brennstoffzusatzzusammensetzungen, die aliphatische amine und polyalkylhydroxyaromate enthalten |
EP0629233A4 (de) * | 1992-12-28 | 1995-08-16 | Chevron Res & Tech | Brennstoffzusatzzusammensetzungen, die aliphatische amine und polyalkylhydroxyaromate enthalten. |
EP0626442A1 (de) * | 1993-05-24 | 1994-11-30 | The Lubrizol Corporation | Mit einem Stockpunkterniedrigtem behandelte Fettsäureester, als biologisch abbaubare Verbrennungsmotorkraftstoffe |
GB2285057B (en) * | 1993-12-23 | 1997-12-10 | Ethyl Petroleum Additives Ltd | Evaporative burner fuels and additives therefor |
GB2285057A (en) * | 1993-12-23 | 1995-06-28 | Ethyl Petroleum Additives Ltd | Evaporative burner fuels and additives therefor |
EP0662507A2 (de) * | 1993-12-23 | 1995-07-12 | Ethyl Petroleum Additives Limited | Verdampfbare Brennstoffe und Zusätze dafür |
EP0662507A3 (de) * | 1993-12-23 | 1995-10-11 | Ethyl Petroleum Additives Ltd | Verdampfbare Brennstoffe und Zusätze dafür. |
US5525127A (en) * | 1993-12-23 | 1996-06-11 | Ethyl Petroleum Additives Limited | Evaporative burner fuels and additives therefor |
US5792735A (en) * | 1994-01-11 | 1998-08-11 | Bp Chemicals (Additives) Limited | Lubricating oil compositions |
US5725611A (en) * | 1994-04-19 | 1998-03-10 | Betzdearborn Inc. | Methods for reducing fouling deposit formation in jet engines |
US5621154A (en) * | 1994-04-19 | 1997-04-15 | Betzdearborn Inc. | Methods for reducing fouling deposit formation in jet engines |
US5596130A (en) * | 1994-04-19 | 1997-01-21 | Betz Laboratories, Inc. | Methods and compositions for reducing fouling deposit formation in jet engines |
EP0678568A1 (de) * | 1994-04-19 | 1995-10-25 | Betz Europe, Inc. | Verfahren und Zusammensetzungen zur Strahltriebwerksverschmutzungsniederschlagsbildungverminderung |
EP1050573A3 (de) * | 1994-12-13 | 2001-01-03 | Infineum USA L.P. | Brennölzusammensetzungen |
WO1996040844A1 (en) * | 1995-06-07 | 1996-12-19 | Orr William C | Vapor phase combustion method and compositions ii |
US5928392A (en) * | 1996-05-14 | 1999-07-27 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
FR2839315A1 (fr) * | 2002-05-03 | 2003-11-07 | Totalfinaelf France | Additif pour ameliorer la stabilite thermique de compositions d'hydrocarbures |
WO2005003265A1 (en) * | 2003-06-25 | 2005-01-13 | The Lubrizol Corporation | Gel additives for fuel that reduce soot and/or emissions from engines |
EP2243816A1 (de) * | 2003-06-25 | 2010-10-27 | The Lubrizol Corporation | Brennstoffgeladditive zur Reduzierung von Russ und/oder Emissionen im Abgas eines Motors |
EP1496100A1 (de) * | 2003-07-08 | 2005-01-12 | Ethyl Petroleum Additives, Inc. | Destillattreibstoffezusammensetzungen zur Verbesserung der Verbrennung und der Motorsauberkeit. |
WO2005087901A2 (en) * | 2004-03-09 | 2005-09-22 | Innospec Limited | Fuel additive composition having antiknock properties |
WO2005087901A3 (en) * | 2004-03-09 | 2006-03-23 | Ass Octel | Fuel additive composition having antiknock properties |
EP1854867A1 (de) | 2006-05-12 | 2007-11-14 | Repsol Ypf S.A. | Neue stabilisierte Kraftstoffzusammensetzung |
EP2147966A1 (de) * | 2008-07-25 | 2010-01-27 | Total Raffinage Marketing | Zusatzstoff für flüssigen Brennstoff, der ihn enthaltende flüssige Brennstoff und seine Anwendung für Energieerzeugungsgeräte und/oder Heizgeräte und/oder Kochgeräte |
FR2934276A1 (fr) * | 2008-07-25 | 2010-01-29 | Total France | Additif pour combustible liquide, combustible liquide le contenant et son utilisation pour les appareils de production d'energie et/ou de chauffage et/ou de cuisson |
WO2012023872A2 (en) | 2010-02-10 | 2012-02-23 | Marine Resources Exploration International B.V. | Synergistic compositions of anti-explosive additives for gasolines |
WO2020117520A1 (en) * | 2018-12-07 | 2020-06-11 | Exxonmobil Research And Engineering Company | Fuel high temperature antioxidant additive |
US10899984B2 (en) | 2018-12-07 | 2021-01-26 | Exxonmobil Research And Engineering Company | Fuel high temperature antioxidant additive |
Also Published As
Publication number | Publication date |
---|---|
CA2051451A1 (en) | 1992-03-21 |
AU634422B2 (en) | 1993-02-18 |
JPH04234490A (ja) | 1992-08-24 |
CA2051451C (en) | 2003-02-04 |
ES2048439T3 (es) | 1994-03-16 |
DE69006029T2 (de) | 1994-05-05 |
DE69006029D1 (de) | 1994-02-24 |
AU8465391A (en) | 1992-03-26 |
JP2965764B2 (ja) | 1999-10-18 |
EP0476197B1 (de) | 1994-01-12 |
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