CA2613952C - Additive composition - Google Patents
Additive composition Download PDFInfo
- Publication number
- CA2613952C CA2613952C CA2613952A CA2613952A CA2613952C CA 2613952 C CA2613952 C CA 2613952C CA 2613952 A CA2613952 A CA 2613952A CA 2613952 A CA2613952 A CA 2613952A CA 2613952 C CA2613952 C CA 2613952C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- composition according
- additive composition
- reaction
- fuel oil
- 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.)
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- 239000000654 additive Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 230000000996 additive effect Effects 0.000 title claims abstract description 33
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- -1 aliphatic aldehyde Chemical class 0.000 claims abstract description 23
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 21
- 239000003623 enhancer Substances 0.000 claims abstract description 19
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 229920001897 terpolymer Polymers 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002576 ketones Chemical class 0.000 claims abstract description 5
- 239000007859 condensation product Substances 0.000 claims abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 26
- 239000000194 fatty acid Substances 0.000 claims description 26
- 229930195729 fatty acid Natural products 0.000 claims description 26
- 150000004665 fatty acids Chemical class 0.000 claims description 26
- 239000000295 fuel oil Substances 0.000 claims description 26
- 239000005864 Sulphur Substances 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003784 tall oil Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 235000010469 Glycine max Nutrition 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 235000019486 Sunflower oil Nutrition 0.000 claims description 4
- 239000002600 sunflower oil Substances 0.000 claims description 4
- 239000010771 distillate fuel oil Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 description 49
- 239000002253 acid Substances 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 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 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 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 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- ADVGKWPZRIDURE-UHFFFAOYSA-N 2'-Hydroxyacetanilide Chemical class CC(=O)NC1=CC=CC=C1O ADVGKWPZRIDURE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical class NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 102100035115 Testin Human genes 0.000 description 1
- 101710070533 Testin Proteins 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 1
- XPKFJIVNCKUXOI-UHFFFAOYSA-N formaldehyde;2-hydroxybenzoic acid Chemical compound O=C.OC(=O)C1=CC=CC=C1O XPKFJIVNCKUXOI-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 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
- 239000010763 heavy fuel oil Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1981—Condensation polymers of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
-
- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/20—Function and purpose of a components of a fuel or the composition as a whole for improving conductivity
-
- 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
- C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
- C10L2300/30—Mixture of three components
Abstract
An additive composition comprises a lubricity enhancer and a conductivity-- improving additive. The lubricity enhancer comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine and the conductivity improving additive comprises the combination of: (a) a polymeric condensation product formed by the reaction of an aliphatic aldehyde or ketone, or a reactive equivalent, with at least one ester of p-hydroxybenzoic acid with, (b) a copolymer, terpolymer or polymer of acrylic acid or methacrylic acid or a derivative thereof.
Description
Additive Composition This invention relates to additive compositions, and to their use to improve the characteristics of fuel oils, especially middle distillate fuels such as diesel fuels, kerosene and jet fuel.
Environmental concerns have led to a need for fuels with reduced sulphur content, especially diesel fuel, heating oil and kerosene. However, the refining processes that produce fuels with low sulphur contents also result in a product of lower viscosity and a lower content of other components in the fuel that contribute to its lubricity, for example, polycyclic aromatics and polar compounds. Furthermore, sulphur-containing compounds in general are regarded as providing some anti-wear properties and a result of the reduction in their proportions, together with the reduction in proportions of other components providing lubricity, has been an increase in the number of reported problems in fuel pumps in diesel engines. The problems are caused by wear in, for example, cam plates, plungers, rollers, spindles and drive shafts, which may result in sudden pump failures relatively early in the life of the engine.
The problems may be expected to become worse in future because, in order to meet stricter requirements on exhaust emissions generally, higher pressure fuel systems, including in-line pumps, rotary pumps, common-rail pumps and unit injector systems, are being introduced, these being expected to have more stringent lubricity requirements than present equipment, at the same time as lower sulphur levels in fuels become more widely required.
Historically, the typical sulphur content in a diesel fuel was below 0.5% by weight.
In Europe maximum sulphur levels have been reduced from 0.20% to 0.05% and in Sweden grades of fuel with levels below 0.005% (Class 2) and 0.001% (Class 1) are in use. A fuel oil composition with a sulphur level below 0.05% by weight is referred to herein as a low-sulphur fuel.
Such low-sulphur fuels may contain an additive to enhance their lubricity.
These additives are of several types. In WO 94/17160, there is disclosed a low sulphur fuel comprising a carboxylic acid ester to enhance lubricity, more especially an ester in which the acid moiety contains from 2 to 50 carbon atoms and the alcohol moiety contains one or more carbon atoms. In U.S. Patent No. 3273981, a mixture of a dimer acid, for example, the dimer of linoleic acid, and a partially esterified polyhydric alcohol is described for the same purpose. In U.S. Patent No. 3287273, the use of an optionally hydrogenated dimer acid glycol ester is described. Other materials used as lubricity enhancers, or anti-wear agents as they are also termed, include a sulphurized dioleyl norbomene ester (EP-A-99595), castor oil (U.S. Patent No. 4375360 and EP-A-605857) and, in methanol-containing fuels, a variety of alcohols and acids having from 6 to 30 carbon atoms, acid and alcohol ethoxylates, mono-and di-esters, polyol esters, and olefin-carboxylic acid copolymers and vinyl alcohol polymers (also U.S. Patent No. 4375360).
EP 0 798 364 Al describes the use of a salt formed by the reaction between a carboxylic acid and an aliphatic amine to improve inter alia, the lubricity of a diesel fuel.
The amines used have hydrocarbyl groups of between 2 and 50 carbon atoms, preferably between 8 and 20 carbon atoms, with amines such as oleyl amine being exemplified.
US 6,277,158 describes a concentrate containing n-butlyamine oleate as a friction modifier for addition to motor gasoline.
US2002/0095858 relates to fuel oil compositions containing an additive formed by the reaction of a mono- or dicarboxylic acid of 6 to 50 carbon atoms with an amine having at least one branched alkyl substituent. These additives are shown to be effective lubricity enhancers for the fuel.
US 2002/0014034 describes the use of additives to improve the lubricity of a fuel oil.
A suitable additive may be formed by the reaction of N, N-dibutylamine with an acid mixture consisting of 70% fatty acids and 30% resin-based acids.
A further consequence of refining processes employed to reduce diesel fuel sulphur and aromatic contents is a reduction in the electrical conductivity of the fuel. The insulating properties of low sulphur fuels represent a potential hazard to refiners, distributors and customers due to the potential for static charge accumulation and discharge.
Static charges can occur during pumping and especially filtration of the fuel, the release of this charge accumulation as a spark constituting a significant risk in highly flammable environments.
Such risks are minimised during fuel processing and handling through appropriate earthing of fuel lines and tanks combined with the use of anti-static additives. These anti-static additives do not prevent the accumulation of static charges but enhance their release to the earthed fuel lines and vessels thereby controlling the risk of sparking. A
number of such additives are in common usage and are available commercially.
It is thus desirable to be able to improve both the lubricity and conductivity of low sulphur content fuels.
EP 1 328 609 describes combinations of either a hydrocarbyl monoamine or an N-hydrocarbyl-substituted poly(alkyleneamine) with either a fatty acid containing 8 to 24 carbon atoms or an ester thereof with an alcohol or polyol of up to 8 carbon atoms.
The present invention is based on the observation of a negative interaction between certain lubricity improving additives and certain conductivity improving additives, and the discovery of combinations of species where this negative interaction is minimised.
Thus in accordance with a first aspect, the present invention provides an additive composition comprising a lubricity enhancer and a conductivity-improving additive;
wherein the lubricity enhancer comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine; and wherein the conductivity improving additive comprises the combination of:
(a) a polymeric condensation product formed by the reaction of an aliphatic aldehyde or ketone, or a reactive equivalent, with at least one ester of p-hydroxybenzoic acid with, (b) a copolymer, terpolymer or polymer of acrylic acid or methacrylic acid or a derivative thereof.
The combination of the lubricity enhancer and the conductivity-improving additive according to the present invention is able to provide both good lubricity and good conductivity to a fuel oil composition. This is in contrast to combinations of the lubricity enhancer with other conductivity-improving additives where a significant loss in conductivity performance has been observed.
In this specification, the use of the term 'salt' to describe the product formed by the reaction of the carboxylic acid and the amine should not be taken to mean that the reaction necessarily forms a pure salt. It is presently believed that the reaction does form a salt and thus that the reaction product contains such as salt however, due to the complexity of the reaction, it is likely that other species will also be present. The term 'salt' should thus be taken to include not only the pure salt species, but also the mixture of species formed during the reaction of the carboxylic acid and the amine.
As carboxylic acid, those corresponding to the formula [R'(COOH)X]y , where each R' is independently a hydrocarbon group of between 2 and 45 carbon atoms, and x is an integer between 1 and 4, are suitable. Preferably, R' is a hydrocarbon group of 8 to 24 carbon atoms, more preferably, 12 to 20 carbon atoms. Preferably, x is 1 or 2, more preferably, x is 1. Preferably, y is 1, in which case the acid has a single R' group.
Alternatively, the acid may be a dimer, trimer or higher oligomer acid, in which case y will be greater than 1 for example 2, 3 or 4 or more. R' is suitably an alkyl or alkenyl group which may be linear or branched. Examples of carboxylic acids which may be used in the present invention include: lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, neodecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, caproleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, coconut oil fatty acid, soy bean fatty acid, tall oil fatty acid, sunflower oil fatty acid, fish oil fatty acid, rapeseed oil fatty acid, tallow oil fatty acid and palm oil fatty acid. Mixtures of two or more acids in any proportion are also suitable. Also suitable are the anhydrides of carboxylic acids, their derivatives and mixtures thereof. In a preferred embodiment, the carboxylic acid comprises tall oil fatty acid (TOFA). It has been found that TOFA with a saturate content of less than 5% by weight is especially suitable. As is known in the art, TOFA contains small but variable amounts of rosin acids and isomers thereof.
Preferably, TOFA with an abietic acid content of less than 5% by weight, for example, less than 2% by weight, is used.
Environmental concerns have led to a need for fuels with reduced sulphur content, especially diesel fuel, heating oil and kerosene. However, the refining processes that produce fuels with low sulphur contents also result in a product of lower viscosity and a lower content of other components in the fuel that contribute to its lubricity, for example, polycyclic aromatics and polar compounds. Furthermore, sulphur-containing compounds in general are regarded as providing some anti-wear properties and a result of the reduction in their proportions, together with the reduction in proportions of other components providing lubricity, has been an increase in the number of reported problems in fuel pumps in diesel engines. The problems are caused by wear in, for example, cam plates, plungers, rollers, spindles and drive shafts, which may result in sudden pump failures relatively early in the life of the engine.
The problems may be expected to become worse in future because, in order to meet stricter requirements on exhaust emissions generally, higher pressure fuel systems, including in-line pumps, rotary pumps, common-rail pumps and unit injector systems, are being introduced, these being expected to have more stringent lubricity requirements than present equipment, at the same time as lower sulphur levels in fuels become more widely required.
Historically, the typical sulphur content in a diesel fuel was below 0.5% by weight.
In Europe maximum sulphur levels have been reduced from 0.20% to 0.05% and in Sweden grades of fuel with levels below 0.005% (Class 2) and 0.001% (Class 1) are in use. A fuel oil composition with a sulphur level below 0.05% by weight is referred to herein as a low-sulphur fuel.
Such low-sulphur fuels may contain an additive to enhance their lubricity.
These additives are of several types. In WO 94/17160, there is disclosed a low sulphur fuel comprising a carboxylic acid ester to enhance lubricity, more especially an ester in which the acid moiety contains from 2 to 50 carbon atoms and the alcohol moiety contains one or more carbon atoms. In U.S. Patent No. 3273981, a mixture of a dimer acid, for example, the dimer of linoleic acid, and a partially esterified polyhydric alcohol is described for the same purpose. In U.S. Patent No. 3287273, the use of an optionally hydrogenated dimer acid glycol ester is described. Other materials used as lubricity enhancers, or anti-wear agents as they are also termed, include a sulphurized dioleyl norbomene ester (EP-A-99595), castor oil (U.S. Patent No. 4375360 and EP-A-605857) and, in methanol-containing fuels, a variety of alcohols and acids having from 6 to 30 carbon atoms, acid and alcohol ethoxylates, mono-and di-esters, polyol esters, and olefin-carboxylic acid copolymers and vinyl alcohol polymers (also U.S. Patent No. 4375360).
EP 0 798 364 Al describes the use of a salt formed by the reaction between a carboxylic acid and an aliphatic amine to improve inter alia, the lubricity of a diesel fuel.
The amines used have hydrocarbyl groups of between 2 and 50 carbon atoms, preferably between 8 and 20 carbon atoms, with amines such as oleyl amine being exemplified.
US 6,277,158 describes a concentrate containing n-butlyamine oleate as a friction modifier for addition to motor gasoline.
US2002/0095858 relates to fuel oil compositions containing an additive formed by the reaction of a mono- or dicarboxylic acid of 6 to 50 carbon atoms with an amine having at least one branched alkyl substituent. These additives are shown to be effective lubricity enhancers for the fuel.
US 2002/0014034 describes the use of additives to improve the lubricity of a fuel oil.
A suitable additive may be formed by the reaction of N, N-dibutylamine with an acid mixture consisting of 70% fatty acids and 30% resin-based acids.
A further consequence of refining processes employed to reduce diesel fuel sulphur and aromatic contents is a reduction in the electrical conductivity of the fuel. The insulating properties of low sulphur fuels represent a potential hazard to refiners, distributors and customers due to the potential for static charge accumulation and discharge.
Static charges can occur during pumping and especially filtration of the fuel, the release of this charge accumulation as a spark constituting a significant risk in highly flammable environments.
Such risks are minimised during fuel processing and handling through appropriate earthing of fuel lines and tanks combined with the use of anti-static additives. These anti-static additives do not prevent the accumulation of static charges but enhance their release to the earthed fuel lines and vessels thereby controlling the risk of sparking. A
number of such additives are in common usage and are available commercially.
It is thus desirable to be able to improve both the lubricity and conductivity of low sulphur content fuels.
EP 1 328 609 describes combinations of either a hydrocarbyl monoamine or an N-hydrocarbyl-substituted poly(alkyleneamine) with either a fatty acid containing 8 to 24 carbon atoms or an ester thereof with an alcohol or polyol of up to 8 carbon atoms.
The present invention is based on the observation of a negative interaction between certain lubricity improving additives and certain conductivity improving additives, and the discovery of combinations of species where this negative interaction is minimised.
Thus in accordance with a first aspect, the present invention provides an additive composition comprising a lubricity enhancer and a conductivity-improving additive;
wherein the lubricity enhancer comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine; and wherein the conductivity improving additive comprises the combination of:
(a) a polymeric condensation product formed by the reaction of an aliphatic aldehyde or ketone, or a reactive equivalent, with at least one ester of p-hydroxybenzoic acid with, (b) a copolymer, terpolymer or polymer of acrylic acid or methacrylic acid or a derivative thereof.
The combination of the lubricity enhancer and the conductivity-improving additive according to the present invention is able to provide both good lubricity and good conductivity to a fuel oil composition. This is in contrast to combinations of the lubricity enhancer with other conductivity-improving additives where a significant loss in conductivity performance has been observed.
In this specification, the use of the term 'salt' to describe the product formed by the reaction of the carboxylic acid and the amine should not be taken to mean that the reaction necessarily forms a pure salt. It is presently believed that the reaction does form a salt and thus that the reaction product contains such as salt however, due to the complexity of the reaction, it is likely that other species will also be present. The term 'salt' should thus be taken to include not only the pure salt species, but also the mixture of species formed during the reaction of the carboxylic acid and the amine.
As carboxylic acid, those corresponding to the formula [R'(COOH)X]y , where each R' is independently a hydrocarbon group of between 2 and 45 carbon atoms, and x is an integer between 1 and 4, are suitable. Preferably, R' is a hydrocarbon group of 8 to 24 carbon atoms, more preferably, 12 to 20 carbon atoms. Preferably, x is 1 or 2, more preferably, x is 1. Preferably, y is 1, in which case the acid has a single R' group.
Alternatively, the acid may be a dimer, trimer or higher oligomer acid, in which case y will be greater than 1 for example 2, 3 or 4 or more. R' is suitably an alkyl or alkenyl group which may be linear or branched. Examples of carboxylic acids which may be used in the present invention include: lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, neodecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, caproleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, coconut oil fatty acid, soy bean fatty acid, tall oil fatty acid, sunflower oil fatty acid, fish oil fatty acid, rapeseed oil fatty acid, tallow oil fatty acid and palm oil fatty acid. Mixtures of two or more acids in any proportion are also suitable. Also suitable are the anhydrides of carboxylic acids, their derivatives and mixtures thereof. In a preferred embodiment, the carboxylic acid comprises tall oil fatty acid (TOFA). It has been found that TOFA with a saturate content of less than 5% by weight is especially suitable. As is known in the art, TOFA contains small but variable amounts of rosin acids and isomers thereof.
Preferably, TOFA with an abietic acid content of less than 5% by weight, for example, less than 2% by weight, is used.
In another preferred embodiment, the carboxylic acid comprises rapeseed oil fatty acid.
In another preferred embodiment, the carboxylic acid comprises soy bean fatty acid.
In another preferred embodiment, the carboxylic acid comprises sunflower oil fatty acid.
Also suitable are aromatic carboxylic acids and their alkyl derivatives as well as aromatic hydroxy acids and their alkyl derivatives. Illustrative examples include benzoic acid, salicylic acid and acids derived from such species.
Preferably, the carboxylic acid has an iodine value of at least 80g/100g, more preferably at least 100 g/100g, for example, at least 130 g/lOOg or at least 150 g/100g.
Particularly preferred embodiments of the present invention are thus where the lubricity enhancer comprises a salt formed by the reaction of Tall oil fatty acid with di-n-butylamine, Rapeseed oil fatty acid with di-n-butylamine, Soy bean fatty acid with di-n-butylamine, and Sunflower oil fatty acid with di-n-butylamine.
The salt may conveniently be produced by mixing the carboxylic acid with the amine.
The order in which one component is added to the other is not important. The molar ratio of the amount of acid to the amount of amine is suitably from 10:1 to 1:10, preferably from 10:1 to 1:2, more preferably from 2:1 to 1:2, for example, around 1:1. In an embodiment, a molar ratio of 1.1:1 to 1:1.1 has been found to be suitable. The reaction may be conducted at room temperature, but is preferably heated gently, for example to 40 C.
These salts are the subject of the present Applicant's co-pending application EP 05270062.2 where in addition to providing good lubricity to fuel oil compositions they were found to display particularly good low temperature properties.
In another preferred embodiment, the carboxylic acid comprises soy bean fatty acid.
In another preferred embodiment, the carboxylic acid comprises sunflower oil fatty acid.
Also suitable are aromatic carboxylic acids and their alkyl derivatives as well as aromatic hydroxy acids and their alkyl derivatives. Illustrative examples include benzoic acid, salicylic acid and acids derived from such species.
Preferably, the carboxylic acid has an iodine value of at least 80g/100g, more preferably at least 100 g/100g, for example, at least 130 g/lOOg or at least 150 g/100g.
Particularly preferred embodiments of the present invention are thus where the lubricity enhancer comprises a salt formed by the reaction of Tall oil fatty acid with di-n-butylamine, Rapeseed oil fatty acid with di-n-butylamine, Soy bean fatty acid with di-n-butylamine, and Sunflower oil fatty acid with di-n-butylamine.
The salt may conveniently be produced by mixing the carboxylic acid with the amine.
The order in which one component is added to the other is not important. The molar ratio of the amount of acid to the amount of amine is suitably from 10:1 to 1:10, preferably from 10:1 to 1:2, more preferably from 2:1 to 1:2, for example, around 1:1. In an embodiment, a molar ratio of 1.1:1 to 1:1.1 has been found to be suitable. The reaction may be conducted at room temperature, but is preferably heated gently, for example to 40 C.
These salts are the subject of the present Applicant's co-pending application EP 05270062.2 where in addition to providing good lubricity to fuel oil compositions they were found to display particularly good low temperature properties.
Component (a) Component (a) is a condensate species derived from an alkyl ester of p-hydroxybenzoic acid. These HydroxyBenzoate-Formaldehyde Condensates are the subject of the present Applicant's co-pending application EP 1 640 438 A and are referred to herein as HBFC.
Preferably, the at least one ester of p-hydroxybenzoic acid comprises; (i) a straight or branched chain Ci - C7 alkyl ester of p-hydroxybenzoic acid; (ii) a branched chain Cg- C16 alkyl ester of p-hydroxybenzoic acid, or; (iii) a mixture of long chain C8 -C18 alkyl esters of p-hydroxybenzoic acid, at least one of said alkyls being branched.
Preferably, the alkyl in (i) is ethyl or n-butyl.
Preferably, the branched alkyl group in (ii) is 2-ethylhexyl or isodecyl.
Conveniently, the molar ratio of the branched ester to the other ester is in the range of5:1 to 1:5.
Condensates of mixed esters may be used, for example mixed ester condensates of n-octyl and 2-ethylhexyl esters of p-hydroxybenzoic acid may be prepared. The ratio of the esters in the mixed condensates may be varied as required. A mixed ester condensate where the molar ratio of 2-ethylhexyl ester to n-octyl ester is 3:1 has been found to be useful.
Mixed ester condensates of more than two ester monomers may also be prepared.
The number average molecular weight of the polymeric condensation products is suitably in the range of 500 to 5000, preferably 1000 to 3000, more preferably 1000 to 2000 Mn.
Other comonomers may be added to the reaction mixture of aldehyde and alkyl ester or mixture of alkyl esters. Some of the polymers described above, for example, that are based on the 2-ethylhexyl ester, are too viscous to be handled conveniently at temperatures they would be used commercially, i.e. ambient to 60 C, unless diluted with a large proportion of solvent. This problem can be overcome by replacing up to 33 mole % of the p-hydroxybenzoic ester or ester mixture used in the condensation reaction with other comonomers in order to modify the physical properties of the polymers whilst still retaining activity. The comonomers are aromatic compounds that are sufficiently reactive to take part in the condensation reaction. They include alkylated, arylated and acylated benzenes such as toluene, xylene, mesitylene, biphenyls and acetophenone. Other comonomers include hydroxy aromatic compounds such as p-hydroxybenzoic acid, acid derivatives of p-hydroxyaromatic acids such as amides and salts, other hydroxyaromatic acids, alkylphenols, naphthols, phenylphenols, acetamidophenols, alkoxyphenols and o-alkylated, o-arylated and o-acylated phenols. The hydroxy compounds should be either di- or mono-functional with regard to the condensation reaction. The hydroxy compounds that are di-functional should be substituted in the para- position whilst those that are mono-functional can be substituted in any position, e.g. 2,4-di-t-butylphenol - these will only incorporate at the end of a polymer chain.
HBFC may be prepared by the reaction between one or more aldehydes or ketones or reactive equivalents with esters of p-hydroxybenzoic acid. The term "reactive equivalent"
means a material that generates an aldehyde under the conditions of the condensation reaction or a material that undergoes the required condensation reaction to produce moieties equivalent to those produced by an aldehyde. Typical reactive equivalents include oligomers or polymers of the aldehyde, acetals or aldehyde solutions.
The aldehyde may be a mono- or di- aldehyde and may contain other functional groups, such as -COOH, and these could be capable of post-reactions in the product. The aldehyde or ketone or reactive equivalent preferably contains 1-8 carbon atoms, particularly preferred are formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, most preferred is formaldehyde. Formaldehyde could be in the form of paraformaldehyde, trioxan or formalin.
HBFC may be prepared by reacting 1 molecular equivalent (M.E.) of the esters of p-hydroxybenzoic acid with about 0.5-2 M.E. of the aldehyde, preferably 0.7-1.3 M.E. and more preferably 0.8-1.2 M.E. of the aldehyde. The reaction is preferably conducted in the presence of a basic or acidic catalyst, more preferably an acidic catalyst, such as p-toluenesulphonic acid. The reaction is conveniently conducted in an inert solvent, such as Exxsol D60 (a non-aromatic, hydrocarbon solvent, having a boiling point of -200 C), the water produced in the reaction being removed by azeotropic distillation. The reaction is typically run at a temperature of 90-200 C, preferably 100-160 C, and may be run under reduced pressure.
Conveniently, the HBFC can be prepared in a 2-step process whereby the esters of p-hydroxybenzoic acid are first prepared in the same reaction vessel that is used for the subsequent condensation reaction. Thus, the ester is prepared from the appropriate alcohol and p-hydroxybenzoic acid in an inert solvent using an acid catalyst such as p-toluenesulphonic acid, continuously removing water produced in the reaction.
Formaldehyde is then added and the condensation reaction conducted as described above to give the desired HBFC.
Preferably, the solvent is a hydrocarbon solvent, such as an aromatic hydrocarbon solvent. Examples of hydrocarbon solvents include petroleum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the 'SOLVESSO' tradename; alcohols and/or esters; and paraffinic hydrocarbons such as hexane and pentane and isoparaffins. The additive concentrate may also contain further additives as required. Such further additives are known in the art and include, for example the following: detergents, antioxidants (to avoid fuel degradation), corrosion inhibitors, dehazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, co-solvents, package compatibilisers, reodourants, additives to improve the regeneration of particulate traps, middle distillate cold flow improvers and other lubricity additives.
Component (b) The copolymers, terpolymers and polymers of acrylic acid or methacrylic acid or a derivative thereof may be branched or linear. Suitable copolymers, terpolymers or polymers of acrylic acid or methacrylic acid or derivatives thereof are those polymers of ethylenically unsaturated monomers such as methacrylic or acrylic acid esters of alcohols having about 1 to 40 carbon atoms, such as methylacrylate, ethylacrylate, n-propylacrylate, lauryl acrylate, stearyl acrylate, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, lauryl methacrylate, stearyl methacrylate, isodecylmethacrylate, 2-ethylhexylmethacrylate and the like. These copolymers, terpolymers and polymers may have number average molecular weights (Mn) of 1,000 to 10,000,000 and preferably the molecular weight range is from about 5,000 to 1,000,000, most preferably 5,000 to 100,000. A mixture of copolymers, terpolymers and polymers of acrylic acid or methacrylic acid may also be used.
In a preferred embodiment, the acrylate or methacrylate monomer or derivative thereof is copolymerized with a nitrogen-containing, amine-containing or amide-containing monomer, or includes nitrogen-containing, amine-containing or amide-containing branches.
This may be achieved by providing the polymer with sites suitable for grafting, and then nitrogen-containing, amine-containing or amide-containing branches, either monomers or macromonomers, are grafted onto the main chain. Transesterification reactions or amidation reactions may also be employed to produce the same products. Preferably, the copolymer, terpolymer or polymer will contain 0.01 to 5 wt.% nitrogen, more preferably 0.02 to 1 wt.%
nitrogen, even more preferably 0.04 to 0.15 wt.% nitrogen.
Examples of amine-containing monomers include: the basic amino substituted olefins such as p-(2-diethylaminoethyl) styrene; basic nitrogen-containing heterocycles having a polymerizable ethylenically unsaturated substituent, such as the vinyl pyridines or the vinyl pyrrolidones; esters of amino alcohols with unsaturated carboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tertiary butylaminoethyl methacrylate or dimethylaminopropyl methacrylate; amides of diamines with unsaturated carboxylic acids, such as dimethylaminopropyl methacrylamide; amides of polyamines with unsaturated carboxylic acids, examples of such polyamines being ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), and higher polyamines, PAM (N = 7,8) and Heavy Polyamine (N>8); morpholine derivatives of unsaturated carboxylic acids, such as N-(aminopropyl)morpholine derivatives; and polymerizable unsaturated basic amines such as allyl amine.
Preferably, the at least one ester of p-hydroxybenzoic acid comprises; (i) a straight or branched chain Ci - C7 alkyl ester of p-hydroxybenzoic acid; (ii) a branched chain Cg- C16 alkyl ester of p-hydroxybenzoic acid, or; (iii) a mixture of long chain C8 -C18 alkyl esters of p-hydroxybenzoic acid, at least one of said alkyls being branched.
Preferably, the alkyl in (i) is ethyl or n-butyl.
Preferably, the branched alkyl group in (ii) is 2-ethylhexyl or isodecyl.
Conveniently, the molar ratio of the branched ester to the other ester is in the range of5:1 to 1:5.
Condensates of mixed esters may be used, for example mixed ester condensates of n-octyl and 2-ethylhexyl esters of p-hydroxybenzoic acid may be prepared. The ratio of the esters in the mixed condensates may be varied as required. A mixed ester condensate where the molar ratio of 2-ethylhexyl ester to n-octyl ester is 3:1 has been found to be useful.
Mixed ester condensates of more than two ester monomers may also be prepared.
The number average molecular weight of the polymeric condensation products is suitably in the range of 500 to 5000, preferably 1000 to 3000, more preferably 1000 to 2000 Mn.
Other comonomers may be added to the reaction mixture of aldehyde and alkyl ester or mixture of alkyl esters. Some of the polymers described above, for example, that are based on the 2-ethylhexyl ester, are too viscous to be handled conveniently at temperatures they would be used commercially, i.e. ambient to 60 C, unless diluted with a large proportion of solvent. This problem can be overcome by replacing up to 33 mole % of the p-hydroxybenzoic ester or ester mixture used in the condensation reaction with other comonomers in order to modify the physical properties of the polymers whilst still retaining activity. The comonomers are aromatic compounds that are sufficiently reactive to take part in the condensation reaction. They include alkylated, arylated and acylated benzenes such as toluene, xylene, mesitylene, biphenyls and acetophenone. Other comonomers include hydroxy aromatic compounds such as p-hydroxybenzoic acid, acid derivatives of p-hydroxyaromatic acids such as amides and salts, other hydroxyaromatic acids, alkylphenols, naphthols, phenylphenols, acetamidophenols, alkoxyphenols and o-alkylated, o-arylated and o-acylated phenols. The hydroxy compounds should be either di- or mono-functional with regard to the condensation reaction. The hydroxy compounds that are di-functional should be substituted in the para- position whilst those that are mono-functional can be substituted in any position, e.g. 2,4-di-t-butylphenol - these will only incorporate at the end of a polymer chain.
HBFC may be prepared by the reaction between one or more aldehydes or ketones or reactive equivalents with esters of p-hydroxybenzoic acid. The term "reactive equivalent"
means a material that generates an aldehyde under the conditions of the condensation reaction or a material that undergoes the required condensation reaction to produce moieties equivalent to those produced by an aldehyde. Typical reactive equivalents include oligomers or polymers of the aldehyde, acetals or aldehyde solutions.
The aldehyde may be a mono- or di- aldehyde and may contain other functional groups, such as -COOH, and these could be capable of post-reactions in the product. The aldehyde or ketone or reactive equivalent preferably contains 1-8 carbon atoms, particularly preferred are formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, most preferred is formaldehyde. Formaldehyde could be in the form of paraformaldehyde, trioxan or formalin.
HBFC may be prepared by reacting 1 molecular equivalent (M.E.) of the esters of p-hydroxybenzoic acid with about 0.5-2 M.E. of the aldehyde, preferably 0.7-1.3 M.E. and more preferably 0.8-1.2 M.E. of the aldehyde. The reaction is preferably conducted in the presence of a basic or acidic catalyst, more preferably an acidic catalyst, such as p-toluenesulphonic acid. The reaction is conveniently conducted in an inert solvent, such as Exxsol D60 (a non-aromatic, hydrocarbon solvent, having a boiling point of -200 C), the water produced in the reaction being removed by azeotropic distillation. The reaction is typically run at a temperature of 90-200 C, preferably 100-160 C, and may be run under reduced pressure.
Conveniently, the HBFC can be prepared in a 2-step process whereby the esters of p-hydroxybenzoic acid are first prepared in the same reaction vessel that is used for the subsequent condensation reaction. Thus, the ester is prepared from the appropriate alcohol and p-hydroxybenzoic acid in an inert solvent using an acid catalyst such as p-toluenesulphonic acid, continuously removing water produced in the reaction.
Formaldehyde is then added and the condensation reaction conducted as described above to give the desired HBFC.
Preferably, the solvent is a hydrocarbon solvent, such as an aromatic hydrocarbon solvent. Examples of hydrocarbon solvents include petroleum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the 'SOLVESSO' tradename; alcohols and/or esters; and paraffinic hydrocarbons such as hexane and pentane and isoparaffins. The additive concentrate may also contain further additives as required. Such further additives are known in the art and include, for example the following: detergents, antioxidants (to avoid fuel degradation), corrosion inhibitors, dehazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, co-solvents, package compatibilisers, reodourants, additives to improve the regeneration of particulate traps, middle distillate cold flow improvers and other lubricity additives.
Component (b) The copolymers, terpolymers and polymers of acrylic acid or methacrylic acid or a derivative thereof may be branched or linear. Suitable copolymers, terpolymers or polymers of acrylic acid or methacrylic acid or derivatives thereof are those polymers of ethylenically unsaturated monomers such as methacrylic or acrylic acid esters of alcohols having about 1 to 40 carbon atoms, such as methylacrylate, ethylacrylate, n-propylacrylate, lauryl acrylate, stearyl acrylate, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, lauryl methacrylate, stearyl methacrylate, isodecylmethacrylate, 2-ethylhexylmethacrylate and the like. These copolymers, terpolymers and polymers may have number average molecular weights (Mn) of 1,000 to 10,000,000 and preferably the molecular weight range is from about 5,000 to 1,000,000, most preferably 5,000 to 100,000. A mixture of copolymers, terpolymers and polymers of acrylic acid or methacrylic acid may also be used.
In a preferred embodiment, the acrylate or methacrylate monomer or derivative thereof is copolymerized with a nitrogen-containing, amine-containing or amide-containing monomer, or includes nitrogen-containing, amine-containing or amide-containing branches.
This may be achieved by providing the polymer with sites suitable for grafting, and then nitrogen-containing, amine-containing or amide-containing branches, either monomers or macromonomers, are grafted onto the main chain. Transesterification reactions or amidation reactions may also be employed to produce the same products. Preferably, the copolymer, terpolymer or polymer will contain 0.01 to 5 wt.% nitrogen, more preferably 0.02 to 1 wt.%
nitrogen, even more preferably 0.04 to 0.15 wt.% nitrogen.
Examples of amine-containing monomers include: the basic amino substituted olefins such as p-(2-diethylaminoethyl) styrene; basic nitrogen-containing heterocycles having a polymerizable ethylenically unsaturated substituent, such as the vinyl pyridines or the vinyl pyrrolidones; esters of amino alcohols with unsaturated carboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tertiary butylaminoethyl methacrylate or dimethylaminopropyl methacrylate; amides of diamines with unsaturated carboxylic acids, such as dimethylaminopropyl methacrylamide; amides of polyamines with unsaturated carboxylic acids, examples of such polyamines being ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA), and higher polyamines, PAM (N = 7,8) and Heavy Polyamine (N>8); morpholine derivatives of unsaturated carboxylic acids, such as N-(aminopropyl)morpholine derivatives; and polymerizable unsaturated basic amines such as allyl amine.
Particularly preferred is a copolymer of a methacrylate ester of a C8-Ci4 alcohol with a methacrylate ester of an N,N-dialkylaminoalkyl alcohol, such as N,N dimethyl-aminoethanol.
In accordance with a second aspect, the present invention provides a fuel oil composition comprising a major proportion of a fuel oil and a minor proportion of an additive composition according to the first aspect. .
As discussed above, it has been observed that there is a negative interaction between certain lubricity improving additives and certain conductivity improving additives. The present invention minimises this negative interaction. Accordingly, in a preferred embodiment of the second aspect, the fuel oil composition has a conductivity which is at least 50%, preferably at least 60% of the conductivity of an equivalent fuel oil composition containing the same quantity of the conductivity-improving additive, in the absence of the lubricity enhancer. In the context of this preferred embodiment it will be understood that the only difference between the fuel composition of the invention and the 'equivalent' fuel oil composition is the absence of the lubricity enhancer. It will also be understood that the percentage of conductivity retained is to be determined using identical measurement conditions, e.g. temperature, measuring apparatus, sample age etc.
Preferably, the fuel oil is e.g., a petroleum-based fuel oil, especially a middle distillate fuel oil. Such distillate fuel oils generally boil within the range of from 110 C to 500 C, e.g. 150 C to 400 C. The fuel oil may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and thermally and/or refinery streams such as catalytically cracked and hydro-cracked distillates.
The most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils. The heating oil may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 wt %, of vacuum gas oil or cracked gas oil or of both.
Other examples of fuel oils include Fischer-Tropsch fuels. Fischer-Tropsch fuels, also known as FT fuels, include those described as gas-to-liquid (GTL) fuels, biomass-to-liquid (BTL) fuels and coal conversion fuels. To make such fuels, syngas (CO +
H2) is first generated and then converted to normal paraffins by a Fischer-Tropsch process.
The normal paraffins may then be modified by processes such as catalytic cracking/reforming or isomerisation, hydrocracking and hydroisomerisation to yield a variety of hydrocarbons such as iso-paraffins, cyclo-paraffins and aromatic compounds. The resulting FT
fuel can be used as such or in combination with other fuel components and fuel types such as those mentioned in this specification. Also suitable are fuels derived from plant or animal sources such as FAME. These may be used alone or in combination with other types of fuel.
Preferably, the fuel oil has a sulphur content of at most 0.05% by weight, more preferably of at most 0.035% by weight, especially of at most 0.015%. Fuels with even lower levels of sulphur are also suitable such as, fuels with less than 50ppm sulphur by weight, preferably less than 20 ppm, for example lOppm or less.
In accordance with a third aspect, the present invention provides the use of an additive composition according to the first aspect to improve the lubricity of a fuel oil having a sulphur content of at most 0.05% by weight, preferably at most 0.035%
by weight, especially of at most 0.0 15%.
Treat rates Preferably, the salt is present in the fuel oil at level of between 5 and 1000ppm by weight based on the weight of the fuel oil, more preferably between 10 and 500ppm, even more preferably between 10 and 250ppm, especially between 10 and 150ppm, for example, between 50 and 150ppm.
Preferably, the ratio of the amount of component (a) to the amount of component (b) in the additive composition is between 9:1 to 1:9, more preferably between 6:1 to 1:6, for example between 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2 or 1:1 based on the molar amounts of active ingredient.
Suitably, the total amount of (a) and (b) present in the fuel oil is between 0.1 and 10,000ppm of active ingredient by weight based on the weight of the fuel oil, preferably between 1 and 500ppm, more preferably between 1 and 100ppm, for example, between 3 and 50ppm.
In accordance with a second aspect, the present invention provides a fuel oil composition comprising a major proportion of a fuel oil and a minor proportion of an additive composition according to the first aspect. .
As discussed above, it has been observed that there is a negative interaction between certain lubricity improving additives and certain conductivity improving additives. The present invention minimises this negative interaction. Accordingly, in a preferred embodiment of the second aspect, the fuel oil composition has a conductivity which is at least 50%, preferably at least 60% of the conductivity of an equivalent fuel oil composition containing the same quantity of the conductivity-improving additive, in the absence of the lubricity enhancer. In the context of this preferred embodiment it will be understood that the only difference between the fuel composition of the invention and the 'equivalent' fuel oil composition is the absence of the lubricity enhancer. It will also be understood that the percentage of conductivity retained is to be determined using identical measurement conditions, e.g. temperature, measuring apparatus, sample age etc.
Preferably, the fuel oil is e.g., a petroleum-based fuel oil, especially a middle distillate fuel oil. Such distillate fuel oils generally boil within the range of from 110 C to 500 C, e.g. 150 C to 400 C. The fuel oil may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and thermally and/or refinery streams such as catalytically cracked and hydro-cracked distillates.
The most common petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils. The heating oil may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 wt %, of vacuum gas oil or cracked gas oil or of both.
Other examples of fuel oils include Fischer-Tropsch fuels. Fischer-Tropsch fuels, also known as FT fuels, include those described as gas-to-liquid (GTL) fuels, biomass-to-liquid (BTL) fuels and coal conversion fuels. To make such fuels, syngas (CO +
H2) is first generated and then converted to normal paraffins by a Fischer-Tropsch process.
The normal paraffins may then be modified by processes such as catalytic cracking/reforming or isomerisation, hydrocracking and hydroisomerisation to yield a variety of hydrocarbons such as iso-paraffins, cyclo-paraffins and aromatic compounds. The resulting FT
fuel can be used as such or in combination with other fuel components and fuel types such as those mentioned in this specification. Also suitable are fuels derived from plant or animal sources such as FAME. These may be used alone or in combination with other types of fuel.
Preferably, the fuel oil has a sulphur content of at most 0.05% by weight, more preferably of at most 0.035% by weight, especially of at most 0.015%. Fuels with even lower levels of sulphur are also suitable such as, fuels with less than 50ppm sulphur by weight, preferably less than 20 ppm, for example lOppm or less.
In accordance with a third aspect, the present invention provides the use of an additive composition according to the first aspect to improve the lubricity of a fuel oil having a sulphur content of at most 0.05% by weight, preferably at most 0.035%
by weight, especially of at most 0.0 15%.
Treat rates Preferably, the salt is present in the fuel oil at level of between 5 and 1000ppm by weight based on the weight of the fuel oil, more preferably between 10 and 500ppm, even more preferably between 10 and 250ppm, especially between 10 and 150ppm, for example, between 50 and 150ppm.
Preferably, the ratio of the amount of component (a) to the amount of component (b) in the additive composition is between 9:1 to 1:9, more preferably between 6:1 to 1:6, for example between 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2 or 1:1 based on the molar amounts of active ingredient.
Suitably, the total amount of (a) and (b) present in the fuel oil is between 0.1 and 10,000ppm of active ingredient by weight based on the weight of the fuel oil, preferably between 1 and 500ppm, more preferably between 1 and 100ppm, for example, between 3 and 50ppm.
The invention will now be described by way of example only.
Preparation of the lubricity enhancer Example 1 Tall oil fatty acid, with a saturate content of ca. 2% and a rosin acid content of ca.
1.8%, (TOFA-1) (50.0g, 173mmoles) was added to a beaker with stirring. Di-n-butylamine (22.36g, 173mmoles) was then added to the beaker. An exotherm of ca. 38.3 C
was measured indicating that the two components reacted. FTIR analysis of the reaction product showed a reduction in the strong carboxylic acid peak at 1710cm"1 compared to the starting acid, and a corresponding appearance of carboxylate antisymmetric and symmetric stretches at 1553 and 1399 cm' as well as the appearance of a broad range of peaks 2300-2600cni 1 assignable to ammonium species. This was a clear indication of the formation of a salt. The flash-point of the reaction product was 67 C.
Example 2 Example I was repeated using a Tall oil fatty acid with a saturate content of ca. 2%
and a rosin acid content of ca. 0.8%, (TOFA-2).
HFRR testin The salts prepared in Examples 1- 4 above were tested in two low-sulphur diesel fuels (details given in Table 1) using the High Frequency Reciprocating Rig (HFRR) test in accordance with BS EN ISO 12156-1 (2000). Results are given in Table 2. The HFRR value for untreated Fuel 1 was 664 m, and that for untreated Fue12 was 518 m.
Preparation of the lubricity enhancer Example 1 Tall oil fatty acid, with a saturate content of ca. 2% and a rosin acid content of ca.
1.8%, (TOFA-1) (50.0g, 173mmoles) was added to a beaker with stirring. Di-n-butylamine (22.36g, 173mmoles) was then added to the beaker. An exotherm of ca. 38.3 C
was measured indicating that the two components reacted. FTIR analysis of the reaction product showed a reduction in the strong carboxylic acid peak at 1710cm"1 compared to the starting acid, and a corresponding appearance of carboxylate antisymmetric and symmetric stretches at 1553 and 1399 cm' as well as the appearance of a broad range of peaks 2300-2600cni 1 assignable to ammonium species. This was a clear indication of the formation of a salt. The flash-point of the reaction product was 67 C.
Example 2 Example I was repeated using a Tall oil fatty acid with a saturate content of ca. 2%
and a rosin acid content of ca. 0.8%, (TOFA-2).
HFRR testin The salts prepared in Examples 1- 4 above were tested in two low-sulphur diesel fuels (details given in Table 1) using the High Frequency Reciprocating Rig (HFRR) test in accordance with BS EN ISO 12156-1 (2000). Results are given in Table 2. The HFRR value for untreated Fuel 1 was 664 m, and that for untreated Fue12 was 518 m.
Fuel 1 Fuel 2 Specification Unit Density kg/m 811.1 858.4 Kv (40 C) cSt 1.942 2.883 Kv (20 C) cSt 2.843 4.597 Cetane No. 58.1 41.9 Sulphur wt% <0.0005 0.0428 Distillation characteristics IBP C 175.0 187.3 10% C 206.1 219.2 50% C 235.2 270.4 95% C 279.1 333.6 FBP C 291.8 347.3 Table 1 Example Treat rate/ppm HFRR in Fuel l/ m HFRR in Fuel 21 m Table 2 Preparation of Component (a) The following synthetic schemes relate to the preparation of some HBFC
compounds which may be used in the present invention. It will be understood that these examples are given merely to illustrate possible preparative routes and as such are not intended to be limiting in any way. The skilled man will be aware of other synthetic methods and will be able to extend the teachings to the preparation of other compounds, which whilst not explicitly described herein, will nonetheless be suitable for use in the present invention.
Example 3 A mixture of p-hydroxybenzoic acid (111 Og), isodecanol (1397g), Exxsol D60 (670g, a non-aromatic, hydrocarbon solvent, bp -200 C), and p-toluenesulphonic acid (43g) was heated to 160 C over 1.5 hours, slowly reducing the pressure to -200mbar. The water produced in the reaction was continuously removed using a Dean and Stark apparatus.
Heating was continued for a total of 4.5 hours and the vacuum released. The reaction mixture was then cooled to -80 C and then to it was added 95% paraformaldehyde (216g).
The mixture was kept at 80-85 C for 2 hours and then heated to 135 C. The pressure was gradually reduced to -120mbar and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for 5 hours and then Solvesso 150 (1500g) was added to dilute the mixture and give a product having a Mn of 1800 and a Mw of 2400.
Example 4 A mixture of p-hydroxybenzoic acid (1109g), 2-ethylhexanol (862g), n-octanol (288g), p-toluenesulphonic acid (43g) and Exxsol D60 (670g) heated to -157 C
over -30 mins, slowly reducing the pressure to -240mbar. Water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for a total of 3.5 hours then the vacuum was released and the mixture cooled to -80 C.
compounds which may be used in the present invention. It will be understood that these examples are given merely to illustrate possible preparative routes and as such are not intended to be limiting in any way. The skilled man will be aware of other synthetic methods and will be able to extend the teachings to the preparation of other compounds, which whilst not explicitly described herein, will nonetheless be suitable for use in the present invention.
Example 3 A mixture of p-hydroxybenzoic acid (111 Og), isodecanol (1397g), Exxsol D60 (670g, a non-aromatic, hydrocarbon solvent, bp -200 C), and p-toluenesulphonic acid (43g) was heated to 160 C over 1.5 hours, slowly reducing the pressure to -200mbar. The water produced in the reaction was continuously removed using a Dean and Stark apparatus.
Heating was continued for a total of 4.5 hours and the vacuum released. The reaction mixture was then cooled to -80 C and then to it was added 95% paraformaldehyde (216g).
The mixture was kept at 80-85 C for 2 hours and then heated to 135 C. The pressure was gradually reduced to -120mbar and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for 5 hours and then Solvesso 150 (1500g) was added to dilute the mixture and give a product having a Mn of 1800 and a Mw of 2400.
Example 4 A mixture of p-hydroxybenzoic acid (1109g), 2-ethylhexanol (862g), n-octanol (288g), p-toluenesulphonic acid (43g) and Exxsol D60 (670g) heated to -157 C
over -30 mins, slowly reducing the pressure to -240mbar. Water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for a total of 3.5 hours then the vacuum was released and the mixture cooled to -80 C.
95% Paraformaldehyde (228g) was then added and the mixture kept at 80-85 C for hours followed by an hour at 95-100 C. It was then heated to 135 C and the pressure was gradually reduced to -120mbar. Water produced in the reaction was continuously removed using a Dean and Stark apparatus. Heating was continued for a total of 5 hours. Solvesso 150 (900g) and 2,4-di-t-butylphenol (500g) were then added to the mixture as diluents to give the final product, which had a Mn of 1150 and a Mw of 1400.
Example 5 (i) A mixture of p-hydroxybenzoic acid (213g), 2-ethylhexanol (220g), xylene (200m1) and p-toluenesulphonic acid (2g) was refluxed at -155 C for 10 hours and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. The mixture was then evaporated under reduced pressure to give 393g of product, i.e. 2-ethylhexyl p-hydroxybenzoate.
(ii) A mixture of the above product (39.7g), 95% paraformaldehyde (4.55g), p-toluenesulphonic acid (0.35g) and heptane (60m1) was heated at 80-85 C for 2 hours. It was then refluxed at -115 C for 9 hours and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. Toluene (60m1) was then added as a diluent to give the product, which had a Mn of 1300 and a Mw of 1750.
Example 6 A mixture consisting of 2-ethylhexyl p-hydroxybenzoate (41.1 g, as produced in Example 7), xylene (8.7g), 95% paraformaldehyde (5.2g), p-toluenesulphonic acid (0.4g) and octane (50m1) was heated to 80-85 C for 2 hours then refluxed at -135 C
for 4.5 hours, continuously removing the water produced in the reaction using a Dean and Stark apparatus.
Toluene (40m1) was then added to dilute the product, which had a Mn of 1000 and a Mw of 1300.
Example 5 (i) A mixture of p-hydroxybenzoic acid (213g), 2-ethylhexanol (220g), xylene (200m1) and p-toluenesulphonic acid (2g) was refluxed at -155 C for 10 hours and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. The mixture was then evaporated under reduced pressure to give 393g of product, i.e. 2-ethylhexyl p-hydroxybenzoate.
(ii) A mixture of the above product (39.7g), 95% paraformaldehyde (4.55g), p-toluenesulphonic acid (0.35g) and heptane (60m1) was heated at 80-85 C for 2 hours. It was then refluxed at -115 C for 9 hours and the water produced in the reaction was continuously removed using a Dean and Stark apparatus. Toluene (60m1) was then added as a diluent to give the product, which had a Mn of 1300 and a Mw of 1750.
Example 6 A mixture consisting of 2-ethylhexyl p-hydroxybenzoate (41.1 g, as produced in Example 7), xylene (8.7g), 95% paraformaldehyde (5.2g), p-toluenesulphonic acid (0.4g) and octane (50m1) was heated to 80-85 C for 2 hours then refluxed at -135 C
for 4.5 hours, continuously removing the water produced in the reaction using a Dean and Stark apparatus.
Toluene (40m1) was then added to dilute the product, which had a Mn of 1000 and a Mw of 1300.
Example 7 A mixture of 2-ethylhexyl p-hydroxybenzoate (37.3g, as produced in Example 7), 2,4-di-t-butylphenol (7.7g), 95% paraformaldehyde (5.65g), 0.45g p-toluenesulphonic acid and octane (25g) was heated to 80-85 C for 2 hours then refluxed at -.135 C
for 5 hours.
The water produced in the reaction was continuously removed using a Dean and Stark apparatus. Solvesso 150 (27g) was then added to dilute the product, which had a Mn of 1250 and a Mw of 2000.
Component (b) Example 8 A high molecular weight (ca. 300,000) polymethacrylate containing ca. 4 wt% of dimethylaminoethylmethacrylate monomers.
Example 9 Isodecyl methacrylate dimethylaminoethylmethacrylate copolymers of -20,000 molecular weight where the content of the aminic monomer was 1.5, 2.5 , 5.0 or 15 wt%.
Conductivity Testing Conductivity testing was carried out using an EmceeTM Digital Conductivity Meter (Model 1152), which has a calibrated range of 0-390 pSm'. The instrument is self calibrating and zeroing and was used in accordance with the user manual. All conductivity measurements were performed at room temperature on 250-300 ml of fuel in a 300 ml, tall glass beaker. The conductivity measurements were made within 2 hours of placing the fuel into the beaker, dosing it with the respective additives and mixing.
Fuel samples were prepared containing the conductivity-improving additives alone and containing both the conductivity-improving additives and the lubricity enhancer of Example 2 at 200ppm by weight. Results are given in Table 3 below. Each sample was tested as soon as it was prepared and again after standing for 7 and 14 days.
Fuel 1 was used.
The results are given as the percentage loss in measured conductivity between the sample containing only the conductivity-improving additive and the sample containing both the conductivity-improving additive and the lubricity enhancer.
Conductivity Treat rate / % loss after 0 % loss after 7 % loss after 14 additive wppm days days days Al 6 28 31 36 Table 3 Conductivity improving additive Al was within the scope of the present invention being a 7:3 molar ratio of the HBFC of Example 3 and the copolymer of Example 9, where the amine content of the copolymer was 15%. Conductivity improving additives C1, C2 and C3 were used for comparative purposes and were respectively; Stadis 450, Stadis 425 which are products of the Octel Corporation, and AS-2010 available from DBM
Chemicals.
It is clear from the data presented that a large negative interaction on fuel conductivity occurs with combinations of the lubricity enhancer and conductivity-improving additives Cl, C2 and C3. On average, these combinations lose 70% or more of the conductivity they have in the absence of the lubricity enhancer.
Contrastingly, conductivity-improving additive Al is much less affected by the presence of the lubricity enhancer.
for 5 hours.
The water produced in the reaction was continuously removed using a Dean and Stark apparatus. Solvesso 150 (27g) was then added to dilute the product, which had a Mn of 1250 and a Mw of 2000.
Component (b) Example 8 A high molecular weight (ca. 300,000) polymethacrylate containing ca. 4 wt% of dimethylaminoethylmethacrylate monomers.
Example 9 Isodecyl methacrylate dimethylaminoethylmethacrylate copolymers of -20,000 molecular weight where the content of the aminic monomer was 1.5, 2.5 , 5.0 or 15 wt%.
Conductivity Testing Conductivity testing was carried out using an EmceeTM Digital Conductivity Meter (Model 1152), which has a calibrated range of 0-390 pSm'. The instrument is self calibrating and zeroing and was used in accordance with the user manual. All conductivity measurements were performed at room temperature on 250-300 ml of fuel in a 300 ml, tall glass beaker. The conductivity measurements were made within 2 hours of placing the fuel into the beaker, dosing it with the respective additives and mixing.
Fuel samples were prepared containing the conductivity-improving additives alone and containing both the conductivity-improving additives and the lubricity enhancer of Example 2 at 200ppm by weight. Results are given in Table 3 below. Each sample was tested as soon as it was prepared and again after standing for 7 and 14 days.
Fuel 1 was used.
The results are given as the percentage loss in measured conductivity between the sample containing only the conductivity-improving additive and the sample containing both the conductivity-improving additive and the lubricity enhancer.
Conductivity Treat rate / % loss after 0 % loss after 7 % loss after 14 additive wppm days days days Al 6 28 31 36 Table 3 Conductivity improving additive Al was within the scope of the present invention being a 7:3 molar ratio of the HBFC of Example 3 and the copolymer of Example 9, where the amine content of the copolymer was 15%. Conductivity improving additives C1, C2 and C3 were used for comparative purposes and were respectively; Stadis 450, Stadis 425 which are products of the Octel Corporation, and AS-2010 available from DBM
Chemicals.
It is clear from the data presented that a large negative interaction on fuel conductivity occurs with combinations of the lubricity enhancer and conductivity-improving additives Cl, C2 and C3. On average, these combinations lose 70% or more of the conductivity they have in the absence of the lubricity enhancer.
Contrastingly, conductivity-improving additive Al is much less affected by the presence of the lubricity enhancer.
Claims (9)
1. An additive composition comprising a lubricity enhancer and a conductivity-improving additive; wherein the lubricity enhancer comprises a salt formed by the reaction of a carboxylic acid with di-n-butylamine; and wherein the conductivity improving additive comprises the combination of:
(a) a polymeric condensation product formed by the reaction of an aliphatic aldehyde or ketone, or a reactive equivalvent, with at least one ester of p-hydroxybenzoic acid with, (b) a copolymer, terpolymer or polymyer of acrylic acid or methacrylic acid or a derivative thereof.
(a) a polymeric condensation product formed by the reaction of an aliphatic aldehyde or ketone, or a reactive equivalvent, with at least one ester of p-hydroxybenzoic acid with, (b) a copolymer, terpolymer or polymyer of acrylic acid or methacrylic acid or a derivative thereof.
2. An additive composition according to claim 1, wherein the carboxylic acid comprises a fatty acid or a mixture of fatty acids.
3. An additive composition according to claim 1, wherein the carboxylic acid comprises tall oil fatty acid, rape seed oil fatty acid, soy bean fatty acid or sunflower oil fatty acid.
4. An additive composition according to any one of claims 1 to 3, wherein the at least one ester of p-hydroxybenzoic acid comprises: (i) a straight or branched chain alkyl ester of p-hydroxybenzoic acid; (ii) a branched chain C8 - C16 alkyl ester of p-hydroxybenzoic acid; or (iii) a mixture of long chain C8 - C18 alkyl esters of p-hydroxybenzoic acid, at least one of said alkyls being branched.
5. An additive composition according to any one of claims 1 to 4, wherein the copolymer, terpolymer or polymer of acrylic acid or methacrylic acid or a derivative thereof is copolymerized with a nitrogen-containing, amine-containing or amide-containing monomer; or includes nitrogen-containing, amine-containing or amide-containing branches.
6. An additive composition according to any one of claims 1 to 5, wherein the reactive equivalent is an oligomer or a polymer of the aliphatic aldehyde, an aliphatic acetal, or an aliphatic aldehyde solution.
7. A fuel oil composition comprising a major proportion of a fuel oil and a minor proportion of an additive composition according to any one of claims 1 to 6.
8. A fuel oil composition according to claim 7, wherein the fuel oil comprises a middle distillate fuel oil having a sulphur content of at most 0.05% by weight.
9. The use of an additive composition according to any one of claims 1 to 6 to improve the lubricity of a fuel oil having a sulphur content of at most 0.05%
by weight.
by weight.
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JP (1) | JP2008150604A (en) |
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US20080060608A1 (en) * | 2006-09-07 | 2008-03-13 | Angela Priscilla Breakspear | Method and use for the prevention of fuel injector deposits |
CN102888258B (en) * | 2012-10-30 | 2014-09-10 | 世纪国宏新能源科技(北京)有限公司 | Power enhancing agent of fuel |
CN103834450A (en) * | 2012-11-22 | 2014-06-04 | 刘碧友 | Low-carbon material high-efficiency renewable fuel |
EP3093332B1 (en) * | 2015-05-14 | 2018-03-14 | Infineum International Limited | Improvements to additive compositions and to fuel oils |
EP3093333B1 (en) * | 2015-05-14 | 2018-03-14 | Infineum International Limited | Improvements to additive compositions and to fuel oils |
CN105400555B (en) * | 2015-12-11 | 2017-08-25 | 广昌达新材料技术服务(深圳)股份有限公司 | A kind of environmentally friendly oil antistatic agent and its application method |
CA3233684A1 (en) * | 2021-10-04 | 2023-04-13 | Innospec Fuel Specialties Llc | Improvements in fuels |
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FR2751982B1 (en) * | 1996-07-31 | 2000-03-03 | Elf Antar France | ONCTUOSITY ADDITIVE FOR ENGINE FUEL AND FUEL COMPOSITION |
FR2772784B1 (en) * | 1997-12-24 | 2004-09-10 | Elf Antar France | ONCTUOSITY ADDITIVE FOR FUEL |
JP2003533585A (en) * | 2000-03-16 | 2003-11-11 | ザ ルブリゾル コーポレイション | Ultra low sulfur diesel fuel containing antistatic lubricating additives |
DE10058356B4 (en) * | 2000-11-24 | 2005-12-15 | Clariant Gmbh | Fuel oils with improved lubricity, containing reaction products of fatty acids with short-chain oil-soluble amines |
ATE491013T1 (en) * | 2003-05-29 | 2010-12-15 | Infineum Int Ltd | A FUEL OIL COMPOSITION |
KR101237628B1 (en) * | 2004-09-17 | 2013-02-27 | 인피늄 인터내셔날 리미티드 | Improvements in fuel oils |
EP1770151A1 (en) * | 2005-09-30 | 2007-04-04 | Infineum International Limited | Additive concentrate |
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