CA2541591A1 - Method of increasing the oxidation stability of biodiesel - Google Patents
Method of increasing the oxidation stability of biodiesel Download PDFInfo
- Publication number
- CA2541591A1 CA2541591A1 CA002541591A CA2541591A CA2541591A1 CA 2541591 A1 CA2541591 A1 CA 2541591A1 CA 002541591 A CA002541591 A CA 002541591A CA 2541591 A CA2541591 A CA 2541591A CA 2541591 A1 CA2541591 A1 CA 2541591A1
- Authority
- CA
- Canada
- Prior art keywords
- tert
- butyl
- butylphenol
- primary antioxidant
- dimethylphenol
- 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.)
- Abandoned
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 136
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 120
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract 8
- 239000000203 mixture Substances 0.000 claims description 39
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 27
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 21
- 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 claims description 20
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 12
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 12
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- NPHAZMSHLCWTNE-UHFFFAOYSA-N 3-tert-butyl-2,5-dimethylphenol Chemical compound CC1=CC(O)=C(C)C(C(C)(C)C)=C1 NPHAZMSHLCWTNE-UHFFFAOYSA-N 0.000 claims description 11
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 10
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- RJKPEKIHHFNMGS-UHFFFAOYSA-N 2,4-ditert-butyl-3-methylphenol Chemical compound CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C RJKPEKIHHFNMGS-UHFFFAOYSA-N 0.000 claims description 8
- ZZZRZBIPCKQDQR-UHFFFAOYSA-N 2,4-ditert-butyl-6-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O ZZZRZBIPCKQDQR-UHFFFAOYSA-N 0.000 claims description 8
- KDBZVULQVCUNNA-UHFFFAOYSA-N 2,5-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(C(C)(C)C)C(O)=C1 KDBZVULQVCUNNA-UHFFFAOYSA-N 0.000 claims description 8
- AFTBJQDQENGCPC-UHFFFAOYSA-N 2,5-ditert-butyl-4-methylphenol Chemical compound CC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C AFTBJQDQENGCPC-UHFFFAOYSA-N 0.000 claims description 8
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 claims description 7
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 claims description 7
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 claims description 6
- VQQLTEBUMLSLFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-nonylphenol Chemical compound CCCCCCCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VQQLTEBUMLSLFJ-UHFFFAOYSA-N 0.000 claims description 6
- BFZOTKYPSZSDEV-UHFFFAOYSA-N 4-butan-2-yl-2,6-ditert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BFZOTKYPSZSDEV-UHFFFAOYSA-N 0.000 claims description 6
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 claims description 6
- MEPYMUOZRROULQ-UHFFFAOYSA-N 4-tert-butyl-2,6-dimethylphenol Chemical compound CC1=CC(C(C)(C)C)=CC(C)=C1O MEPYMUOZRROULQ-UHFFFAOYSA-N 0.000 claims description 6
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 claims description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- BGRKGHSKCFAPCL-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC=C1O BGRKGHSKCFAPCL-UHFFFAOYSA-N 0.000 claims description 5
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 5
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- JKFZLMPBXBMSPD-UHFFFAOYSA-N 2-butan-2-yl-4-tert-butylphenol Chemical compound CCC(C)C1=CC(C(C)(C)C)=CC=C1O JKFZLMPBXBMSPD-UHFFFAOYSA-N 0.000 claims description 4
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 4
- SDNVJMZXSOXXQN-UHFFFAOYSA-N 3,4-ditert-butyl-2-methylphenol Chemical compound CC1=C(O)C=CC(C(C)(C)C)=C1C(C)(C)C SDNVJMZXSOXXQN-UHFFFAOYSA-N 0.000 claims description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- JJULABXIXFRDCQ-UHFFFAOYSA-N 2,3,4-tritert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C JJULABXIXFRDCQ-UHFFFAOYSA-N 0.000 claims 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims 1
- FHTGJZOULSYEOB-UHFFFAOYSA-N 2,6-di(butan-2-yl)phenol Chemical compound CCC(C)C1=CC=CC(C(C)CC)=C1O FHTGJZOULSYEOB-UHFFFAOYSA-N 0.000 claims 1
- MIHQWNKDHBLQEZ-UHFFFAOYSA-N 3-tert-butyl-2-methylphenol Chemical compound CC1=C(O)C=CC=C1C(C)(C)C MIHQWNKDHBLQEZ-UHFFFAOYSA-N 0.000 claims 1
- OXPSEZLCVXHNQE-UHFFFAOYSA-N 4-tert-butyl-2,3-dimethylphenol Chemical compound CC1=C(C)C(C(C)(C)C)=CC=C1O OXPSEZLCVXHNQE-UHFFFAOYSA-N 0.000 claims 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 claims 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 13
- 238000005809 transesterification reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019484 Rapeseed oil Nutrition 0.000 description 6
- 235000019486 Sunflower oil Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 239000002600 sunflower oil Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 3
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008162 cooking oil Substances 0.000 description 3
- 239000003346 palm kernel oil Substances 0.000 description 3
- 235000019865 palm kernel oil Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- -1 unsaturated fatty acid esters Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- ZRDUANIDHBCCAO-UHFFFAOYSA-N (2,4-ditert-butylphenyl)methanol Chemical compound CC(C)(C)C1=CC=C(CO)C(C(C)(C)C)=C1 ZRDUANIDHBCCAO-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 241000221089 Jatropha Species 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000003490 Thiodipropionic acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 235000014541 cooking fats Nutrition 0.000 description 2
- RHMZKSWPMYAOAZ-UHFFFAOYSA-N diethyl peroxide Chemical class CCOOCC RHMZKSWPMYAOAZ-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000015073 liquid stocks Nutrition 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Natural products C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
- E03D1/02—High-level flushing systems
- E03D1/14—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
- C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
- E03D1/30—Valves for high or low level cisterns; Their arrangement ; Flushing mechanisms in the cistern, optionally with provisions for a pre-or a post- flushing and for cutting off the flushing mechanism in case of leakage
- E03D1/34—Flushing valves for outlets; Arrangement of outlet valves
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D5/00—Special constructions of flushing devices, e.g. closed flushing system
- E03D5/10—Special constructions of flushing devices, e.g. closed flushing system operated electrically, e.g. by a photo-cell; also combined with devices for opening or closing shutters in the bowl outlet and/or with devices for raising/or lowering seat and cover and/or for swiveling the bowl
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
- E03D1/02—High-level flushing systems
- E03D1/14—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves
- E03D2001/147—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves having provisions for active interruption of flushing
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Abstract
The invention relates to a method of increasing the oxidation stability of biodiesel, which comprises adding a primary antioxidant having a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure (see formula I) where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or
Description
METHOD OF INCREASING THE OXIDATION STABILITY OF BIODIESEL
FIELD OF THE INVENTION
The invention relates to a method of increasing the oxidation stability of biodiesel.
BACKGROUND TO THE INVENTION
s An alternative to conventional diesel fuel which is being used to an increasing extent today is biodiesel, which comprises monoalkyl esters of vegetable oils, animal fats and also used cooking fats. Biodiesel is obtained by the transesterification of oils, for example rapeseed oil, soybean oil or sunflower oil and also used cooking oils, with an alcohol in the presence of a catalyst.
to Since the importance of biodiesel as an alternative diesel fuel for passenger cars has been continually increasing in recent times, the production of biodiesel has also increased to a corresponding extent in recent years. Biodiesel has a high content of unsaturated fatty acid esters which can easily be oxidized by atmospheric oxygen. The products formed is (including acids, resins) can lead to corrosion and blockages in injection pumps and/or fuel lines. The increasing use of the alternative biodiesel as automobile fuel has led to a need for oxidation-stabilized biodiesel. According to the prior art, preference is given to adding 2,6-di-tert-butyl-4-methylphenol (BHT) as primary antioxidant to the biodiesel in order to meet the oxidation stability requirements of the standard DIN EN 14214.
The use of 2,6-di-tert-butyl-4-methylphenol as antioxidant is described in European Patent EP 0 189 049. Here, the use of 2,6-di-tert-butyl-4-methylphenol in amounts of from 10 to 100 ppm as exclusive stabilizer in methyl esters of palm kernel oil having from 12 to 18 carbon atoms in the fatty acid is described.
2s DE 102 52 714 and WO 2004/044104, too, describe a method of increasing the oxidation stability of biodiesel by addition of di-2,6-tent-butyl-4-hydroxytoluene. A
liquid stock solution containing from 15 to 60% by weight of monoalkylhydroxytoluene or dialkylhydroxytoluene dissolved in biodiesel is added to the biodiesel to be stabilized to give a concentration of 0.005 3o to 2% by weight of monoalkylhydroxytoluene or dialkylhydroxytoluene, based on the total solution in biodiesel.
FIELD OF THE INVENTION
The invention relates to a method of increasing the oxidation stability of biodiesel.
BACKGROUND TO THE INVENTION
s An alternative to conventional diesel fuel which is being used to an increasing extent today is biodiesel, which comprises monoalkyl esters of vegetable oils, animal fats and also used cooking fats. Biodiesel is obtained by the transesterification of oils, for example rapeseed oil, soybean oil or sunflower oil and also used cooking oils, with an alcohol in the presence of a catalyst.
to Since the importance of biodiesel as an alternative diesel fuel for passenger cars has been continually increasing in recent times, the production of biodiesel has also increased to a corresponding extent in recent years. Biodiesel has a high content of unsaturated fatty acid esters which can easily be oxidized by atmospheric oxygen. The products formed is (including acids, resins) can lead to corrosion and blockages in injection pumps and/or fuel lines. The increasing use of the alternative biodiesel as automobile fuel has led to a need for oxidation-stabilized biodiesel. According to the prior art, preference is given to adding 2,6-di-tert-butyl-4-methylphenol (BHT) as primary antioxidant to the biodiesel in order to meet the oxidation stability requirements of the standard DIN EN 14214.
The use of 2,6-di-tert-butyl-4-methylphenol as antioxidant is described in European Patent EP 0 189 049. Here, the use of 2,6-di-tert-butyl-4-methylphenol in amounts of from 10 to 100 ppm as exclusive stabilizer in methyl esters of palm kernel oil having from 12 to 18 carbon atoms in the fatty acid is described.
2s DE 102 52 714 and WO 2004/044104, too, describe a method of increasing the oxidation stability of biodiesel by addition of di-2,6-tent-butyl-4-hydroxytoluene. A
liquid stock solution containing from 15 to 60% by weight of monoalkylhydroxytoluene or dialkylhydroxytoluene dissolved in biodiesel is added to the biodiesel to be stabilized to give a concentration of 0.005 3o to 2% by weight of monoalkylhydroxytoluene or dialkylhydroxytoluene, based on the total solution in biodiesel.
DE 102 52 715 describes a method of increasing the storage stability of biodiesel, in which a liquid stock solution containing from 15 to 60% by weight of 2,4-di-tert-butylhydroxytoluene dissolved in biodiesel is added to the biodiesel to be stabilized to give a concentration of from 0.005 to 2% by weight of 2,4-di-tert-butylhydroxytoluene, based on the total solution in s biodiesel.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved method of increasing the oxidation stability of biodiesel. In particular, it is an object of the invention to improve the processability of the primary antioxidant in biodiesel and thus improve the economics or the 1 o use of primary antioxidants in biodiesel.
It has surprisingly been found that the addition of a liquid primary antioxidant based on substituted alkylphenols having the structure I to biodiesel makes it possible to improve the handleability of the primary antioxidants in biodiesel. The primary antioxidant used in the is method of the invention has a low melting point, i.e. a melting point of less than or equal to 40°C. Owing to its low melting point, this primary antioxidant can, in the method of the invention, be mixed as a liquid directly into the biodiesel without this primary antioxidant f rstly having to be dissolved in a solvent, for example alcohol, or in biodiesel.
Thus, the preparation of a masterbatch of this primary antioxidant in biodiesel can be dispensed with. The 2o masterbatches are generally prepared using the biodiesel for which the masterbatch is ready to be used. In the case of large distances between biodiesel and antioxidant manufacturers in particular, this leads to high costs for storage and transport in the case of primary antioxidants according to the prior art. The primary antioxidant used in the method of the invention thus leads to low production costs for the oxidation-stabilized biodiesel, since, firstly, the 25 preparation of solutions or masterbatches comprising the active ingredient primary antioxidant can be dispensed with and, secondly, the present method shows that a product mixture from the manufacturing process of substituted alkylphenols can be used without complicated separation and purification steps. A further advantage of the method of the invention is that the production of the oxidation-stabilized biodiesel can be carried out at low temperatures and within a 3o relatively short time. The method of the invention thus makes it possible to improve the economics of the production of oxidation-stabilized biodiesel. The active content of the liquid primary antioxidant used according to the present invention is 100% compared to 20% of the liquid primary antioxidants according to the prior art, since the liquid generally contains only ~ 23443-928 about 20o by weight of the active ingredient antioxidant.
The use of a liquid primary antioxidant according to the method of the invention likewise enables transport and storage costs to be saved as a result of the high active content of primary antioxidant per liter. The use of a liquid primary antioxidant according to the method of the invention also leads to reduced crystallization of the primary antioxidant in the biodiesel or in plant components at low temperatures.
The present invention provides a method of increasing the oxidation stability of biodiesel, which comprises adding a primary antioxidant having a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure I
R
R t I
\R2 where:
R1 and RZ are the same as or different from each other and are hydrogen, a linear C1-C2o alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-C2o alkyl group, and Rq is hydrogen or a linear C1-Cqo alkyl group.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved method of increasing the oxidation stability of biodiesel. In particular, it is an object of the invention to improve the processability of the primary antioxidant in biodiesel and thus improve the economics or the 1 o use of primary antioxidants in biodiesel.
It has surprisingly been found that the addition of a liquid primary antioxidant based on substituted alkylphenols having the structure I to biodiesel makes it possible to improve the handleability of the primary antioxidants in biodiesel. The primary antioxidant used in the is method of the invention has a low melting point, i.e. a melting point of less than or equal to 40°C. Owing to its low melting point, this primary antioxidant can, in the method of the invention, be mixed as a liquid directly into the biodiesel without this primary antioxidant f rstly having to be dissolved in a solvent, for example alcohol, or in biodiesel.
Thus, the preparation of a masterbatch of this primary antioxidant in biodiesel can be dispensed with. The 2o masterbatches are generally prepared using the biodiesel for which the masterbatch is ready to be used. In the case of large distances between biodiesel and antioxidant manufacturers in particular, this leads to high costs for storage and transport in the case of primary antioxidants according to the prior art. The primary antioxidant used in the method of the invention thus leads to low production costs for the oxidation-stabilized biodiesel, since, firstly, the 25 preparation of solutions or masterbatches comprising the active ingredient primary antioxidant can be dispensed with and, secondly, the present method shows that a product mixture from the manufacturing process of substituted alkylphenols can be used without complicated separation and purification steps. A further advantage of the method of the invention is that the production of the oxidation-stabilized biodiesel can be carried out at low temperatures and within a 3o relatively short time. The method of the invention thus makes it possible to improve the economics of the production of oxidation-stabilized biodiesel. The active content of the liquid primary antioxidant used according to the present invention is 100% compared to 20% of the liquid primary antioxidants according to the prior art, since the liquid generally contains only ~ 23443-928 about 20o by weight of the active ingredient antioxidant.
The use of a liquid primary antioxidant according to the method of the invention likewise enables transport and storage costs to be saved as a result of the high active content of primary antioxidant per liter. The use of a liquid primary antioxidant according to the method of the invention also leads to reduced crystallization of the primary antioxidant in the biodiesel or in plant components at low temperatures.
The present invention provides a method of increasing the oxidation stability of biodiesel, which comprises adding a primary antioxidant having a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure I
R
R t I
\R2 where:
R1 and RZ are the same as or different from each other and are hydrogen, a linear C1-C2o alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-C2o alkyl group, and Rq is hydrogen or a linear C1-Cqo alkyl group.
The invention further provides for the use of a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure Rz OH
R ;t < I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-CZO alkyl group or RS' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-Czo alkyl group, and R4 is hydrogen or a linear C1-CQO alkyl group.
The invention likewise provides an oxidation-stabilized biodiesel comprising from 10 to 20,000 ppm (w/w) of a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure R Ri I
\R2 where:
R1 and RZ are the same as or different from each other and are hydrogen, a linear C1-C2o alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, 5 R3 and RS are the same as or different from each other and are hydrogen or a linear C1-CZO alkyl group, and Rq is hydrogen or a linear C1-C9o alkyl group.
DETAILED DESCRIPTION OF THE INVENTION
The method of increasing the oxidation stability of biodiesel comprises adding a primary antioxidant having a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure ~ R3 OH
Rt RS
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-CZO alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-CZO alkyl group, and R4 is hydrogen or a linear C1-C4o alkyl group.
5a For the purposes of the present invention, primary antioxidants are compounds or mixtures of compounds which inhibit or prevent undesirable degradation reactions in the biodiesel caused by oxygen. The mode of action of these primary antioxidants in the biodiesel is described in the following reaction scheme, where R and R' are each an organic radical and AOH is a primary antioxidant used in the method of the invention.
1. Chain initiation O.Z. 6496 R H ~ R' + H ' R H + 02 ~ R' + H02' 2. Chain propagation R' + 02 ---~ R02.
R02 ' + R' H --~ ROOH + R' ' 3. Chain termination R02' + AOH ---~ ROOH + AO ' AO ' + R' ~ AOR
Apart from the abovementioned reactions, it is also possible for reactions on the double bonds of the alkyl esters of fatty acids, which can likewise be initiated by oxygen, to occur. Here, the carbon-hydrogen bond which is located in the allyl position relative to the double bond is to preferentially attacked by the oxygen:
H H
The primary antioxidant used in the method of the invention comprises neither organic solvents, for example alcohols, nor biodiesel, as is the case, for example, when a masterbatch is 1 s employed. The primary antioxidant used therefore preferably comprises exclusively alkylphenols and/or substituted alkylphenols. In particular, a mixture comprising various substituted and/or unsubstituted alkylphenols, preferably a mixture comprising from 0.1 to 99.9% by weight, preferably from 50 to 99% by weight and particularly preferably from 55 to 90% by weight, of one or more compounds having the structure I, is used as primary 2o antioxidant in the method of the invention.
R ;t < I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-CZO alkyl group or RS' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-Czo alkyl group, and R4 is hydrogen or a linear C1-CQO alkyl group.
The invention likewise provides an oxidation-stabilized biodiesel comprising from 10 to 20,000 ppm (w/w) of a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure R Ri I
\R2 where:
R1 and RZ are the same as or different from each other and are hydrogen, a linear C1-C2o alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, 5 R3 and RS are the same as or different from each other and are hydrogen or a linear C1-CZO alkyl group, and Rq is hydrogen or a linear C1-C9o alkyl group.
DETAILED DESCRIPTION OF THE INVENTION
The method of increasing the oxidation stability of biodiesel comprises adding a primary antioxidant having a melting point of less than or equal to 40°C to the biodiesel to be stabilized in an amount of from 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure ~ R3 OH
Rt RS
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-CZO alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and RS are the same as or different from each other and are hydrogen or a linear C1-CZO alkyl group, and R4 is hydrogen or a linear C1-C4o alkyl group.
5a For the purposes of the present invention, primary antioxidants are compounds or mixtures of compounds which inhibit or prevent undesirable degradation reactions in the biodiesel caused by oxygen. The mode of action of these primary antioxidants in the biodiesel is described in the following reaction scheme, where R and R' are each an organic radical and AOH is a primary antioxidant used in the method of the invention.
1. Chain initiation O.Z. 6496 R H ~ R' + H ' R H + 02 ~ R' + H02' 2. Chain propagation R' + 02 ---~ R02.
R02 ' + R' H --~ ROOH + R' ' 3. Chain termination R02' + AOH ---~ ROOH + AO ' AO ' + R' ~ AOR
Apart from the abovementioned reactions, it is also possible for reactions on the double bonds of the alkyl esters of fatty acids, which can likewise be initiated by oxygen, to occur. Here, the carbon-hydrogen bond which is located in the allyl position relative to the double bond is to preferentially attacked by the oxygen:
H H
The primary antioxidant used in the method of the invention comprises neither organic solvents, for example alcohols, nor biodiesel, as is the case, for example, when a masterbatch is 1 s employed. The primary antioxidant used therefore preferably comprises exclusively alkylphenols and/or substituted alkylphenols. In particular, a mixture comprising various substituted and/or unsubstituted alkylphenols, preferably a mixture comprising from 0.1 to 99.9% by weight, preferably from 50 to 99% by weight and particularly preferably from 55 to 90% by weight, of one or more compounds having the structure I, is used as primary 2o antioxidant in the method of the invention.
Particular preference is given to using a mixture comprising exclusively compounds having the structure I as primary antioxidant in the method of the invention. This mixture has the advantage that it comprises exclusively compounds having the structure I which all have an oxidation-stabilizing action on biodiesel.
In the method of the invention, preference is given to using a primary antioxidant comprising at least one compound having the structure II
R_' I I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-Cq alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C9 alkyl group, and R4 is hydrogen or a linear C1-C4 alkyl group.
Preference is given to adding a primary antioxidant comprising at least one compound having the structure III
OH
~H3C)3C C(CH3)3 \ III
to the biodiesel in the method of the invention.
O.Z. 6496 Particular preference is given to adding a primary antioxidant comprising at least one compound having the structure IV
(H3G
IV
s to the biodiesel in the method of the invention.
Furthermore, the primary antioxidant used in the method of the invention can comprise exclusively compounds selected from among to - tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol, - di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, i s - tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tent-butylphenol, 4-tent-butylphenol, 20 - di-sec-butylphenols, - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tent-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, tent-amylphenols, in particular 2-tert-amylphenol, , ' - di-tert-amylphenols, in particular 2,4-di-tert-amylphenol, 2s - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and/or octadecylphenol, and mixtures of these compounds, with this primary antioxidant having a melting point of less than or equal to 40°C.
In the method of the invention, preference is given to using a primary antioxidant comprising at least one compound having the structure II
R_' I I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-Cq alkyl group or Rs' \* , where * is a carbon atom of the aromatic ring system, R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C9 alkyl group, and R4 is hydrogen or a linear C1-C4 alkyl group.
Preference is given to adding a primary antioxidant comprising at least one compound having the structure III
OH
~H3C)3C C(CH3)3 \ III
to the biodiesel in the method of the invention.
O.Z. 6496 Particular preference is given to adding a primary antioxidant comprising at least one compound having the structure IV
(H3G
IV
s to the biodiesel in the method of the invention.
Furthermore, the primary antioxidant used in the method of the invention can comprise exclusively compounds selected from among to - tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol, - di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, i s - tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tent-butylphenol, 4-tent-butylphenol, 20 - di-sec-butylphenols, - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tent-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, tent-amylphenols, in particular 2-tert-amylphenol, , ' - di-tert-amylphenols, in particular 2,4-di-tert-amylphenol, 2s - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and/or octadecylphenol, and mixtures of these compounds, with this primary antioxidant having a melting point of less than or equal to 40°C.
Pure substances or mixtures which are or comprise compounds having the structure I to IV and have a melting point of greater than 40°C are excluded from the present invention.
The primary antioxidant used in the method of the invention has a melting point of <- 40°C, preferably <- 39°C
and particularly preferably <- 38°C.
Particularly preferred primary antioxidants include mixtures of:
(1) 2,6-di-tert-butylphenol and other alkylphenols in which the content of 2,6-di-tert-butylphenol is at least 75o by weight, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols in which the content of 6-tert-butyl-2,4-dimethylphenol is at least 75% by weight, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols in which the total content of the first two members is at least 70o by weight.
Secondary antioxidants which can be used in the method of the invention are alkylthiomethylphenols, preferably selected from among 9a - 2,4-di((octylthio)methyl)-6-tert-butylphenol, - 2,4-di((octylthio)methyl)-6-methylphenol, - 2,4-di((octylthio)methyl)-6-ethylphenol and - 2,6-di((dodecylthio)methyl)-4-nonylphenol, s hydroxylated diphenyl thioethers, preferably selected from among - 2,2'-thiobis[6-tert-butyl-4-methylphenol], - 2,2'-thiobis[4-octylphenol], - 4,4'-thiobis[6-tert-butyl-3-methylphenol], - 4,4'-thiobis[6-tert-butyl-2-methylphenol], to - 4,4'-thiobis[3,6-di-sec-amylphenol] and - 4,4'-bas[2,6-dimethyl-4-hydroxyphenyl]disulfide, phosphates or phosphonites, preferably selected from among - triphenyl phosphate, - diphenyl alkyl phosphates, is - phenyl dialkyl phosphates, - tris[nonylphenyl] phosphate, - trilauryl phosphate, - trioctadecyl phosphate, - distearyl pentaerythrityl diphosphite, 20 - tris[2,4-di-tert-butylphenyl] phosphate, diisodecyl pentaerythrityl diphosphite, - bas[2,4-di-tert-butylphenyl] pentaerytlu-ityl diphosphite, - bas[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite, - bas[isodecyloxy] pentaerythrityl diphosphite, O.Z. 6496 - bis[2,4-di-tert-butyl-6-methylphenyl] pentaerythrityl diphosphite, - bis[2,4,6-tri-tent-butylphenyl] pentaerythrityl diphosphite, - tristearyl sorbitol triphosphite, - tetrakis[2,4-di-tert-butylphenyl] 4,4'-biphenylenediphosphonite, s - 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, - 6-fluoro-2,4,8,10-tetra-tent-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, - bis[2,4-di-tert-butyl-6-methylphenyl] methyl phosphite and - bis[2,4-di-tert-butyl-6-methylphenyl] ethyl phosphite, or peroxide-destroying compounds, preferably selected from among - esters of (3-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, - the zinc salt of 2-mercaptobenzimidazole, - zinc dibutyldithiocarbamate, - dioctadecyl disulfide and Is - pentaeryfhrityl tetrakis[(3-dodecylmercapto]propionate, or mixtures of these compounds.
For the purposes of the present invention, the term biodiesel encompasses all the saturated and/or unsaturated alkyl esters of fatty acids, in particular methyl or ethyl esters of fatty acids, 2o which can be used as energy carriers. For the purposes of the present invention, energy carriers include both fuels as sources of heat, for example heating material, and fuels for powering vehicles, for example automobiles, goods vehicles, ships or aircraft. The biodiesel to which the method of the invention is applied is preferably a biodiesel which is usually marketed under the name biodiesel for use as automobile fuel. In particular, the biodiesel to which the method of 2s the invention is applied comprises C12-Cza fatty acid alkyl esters, preferably C12-C2a fatty acid methyl esters or C12-Caa fatty acid ethyl esters, which can be present in pure form or as a mixture. In addition, the biodiesel to which the method of the invention is applied can further comprise all customary additives such as secondary antioxidants, antifoams, low-temperature flow improvers. The method of the invention is preferably applied to biodiesel produced from 3o vegetable and/or animal oils by a process of transesterification with an alcohol, preferably methanol or ethanol, particularly preferably methanol. The method of the invention is more preferably applied to biodiesel comprising transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil, cotton seed oil, peanut oil, maize oil and/or used cooking oils. However, particular preference is given to using biodiesel which is obtained from rapeseed oil, sunflower oil or soybean oil by means of the abovementioned transesterification. The method of the invention can also be applied to mixtures of the trans-s esterification products of various vegetable and/or animal oils.
In a particular embodiment of the method of the invention, mixtures of saturated and/or unsaturated fatty acid alkyl esters with liquid energy carriers, for example mineral diesel fuel or heating oil, can be used as biodiesel. Particular preference is given to using a mixture of to mineral diesel fuel and from 0.1 to 99.9% by volume, in particular from 2 to 10% by volume and preferably from 3 to 5% by volume, of saturated and/or unsaturated fatty acid alkyl esters.
In a subsequent step of the method of the invention, the oxidation-stabilized biodiesel can be added in an amount of from 0.1 to 99.9% by volume, in particular from 1 to 20%
by volume, preferably from 2 to 10% by volume and more preferably from 3 to 5% by volume, to a liquid is energy carrier, in particular mineral diesel fuel or heating oil.
In the method of the invention, the primary antioxidant is preferably added directly, in particular in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and more preferably from 100 to 8,000 ppm (w/w). For the purposes of the present 2o invention, direct addition means that no preparation of a solution or a masterbatch of the primary antioxidant ha.s been carried out in a preceding step. In this step, secondary antioxidants can also be added in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and preferably from 100 to 8,000 ppm (w/w), to the biodiesel.
2s The primary antioxidant is preferably dissolved in the biodiesel with stirnng at a temperature of from 18°C to 60°C, more preferably from 20°C to 40°C.
The invention further provides for the use of a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I for 3o increasing the oxidation stability of biodiesel.
Particular preference is given to using a mixture comprising exclusively compounds having the structure I as primary antioxidant. This mixtur a has the advantage that it comprises exclusively O.Z. 6496 compounds having the structure I which alI have an oxidation-stabilizing action on biodiesel.
Preference is given to using a primary antioxidant comprising at least one compound having the structure II. However, greater preference is given to using a primary antioxidant comprising at least one compound having the structure III. Particular preference is given to s using a primary antioxidant comprising at least one compound having the structure IV.
Furthermore, it is possible to use a primary antioxidant comprising exclusively compounds selected from among - tri-tent-butylphenols, in particular 2,4,6-tri-tent-butylphenol, to - di-tent-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, - tert-butylmethylphenols, in particular 2-tent-butyl-4-methylphenol, 6-tent-butyl-2-1 s methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol, - di-sec-butylphenols, 20 - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, - tert-amylphenols, in particular 2-tert-amylphenol, - di-tent-amylphenols, in particular 2,4-di-tert-amylphenol, - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-Zs dodecylphenol and/or octadecylphenol, and mixtures of these compounds, with this primary antioxidant having a melting point of less than or equal to 40°C.
Pure substances or mixtures which are or comprise compounds having the structures I to IV
3o and have a melting point of greater than 40°C are excluded from the present invention.
The oxidation-stabilized biodiesel of the invention comprises from 10 to 20 000 ppm (w/w), preferably from 50 to 12 000 ppm (w/w) and more preferably from 100 to 8000 ppm (w/w), of O.Z. 6496 a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I.
The primary antioxidant of the oxidation-stabilized biodiesel of the invention therefore s preferably comprises exclusively alkyphenols and/or substituted alkylphenols. In particular, the oxidation-stabilized biodiesel of the invention comprises a mixture of various substituted and/or unsubstituted alkylphenols as primary antioxidant. The biodiesel of the present invention preferably comprises a primary antioxidant comprising from 0.1 to 99.9% by weight, more preferably from 50 to 99% by weight and particularly preferably from 55 to 99% by io weight, of one or more compounds having the structure I. The biodiesel of the invention particularly preferably comprises a mixture comprising exclusively compounds having the structure I as primary antioxidant.
The biodiesel of the invention preferably comprises a primary antioxidant comprising at least is one compound having the structure II. The biodiesel of the invention more preferably comprises a primary antioxidant comprising at least one compound having the structure III.
The biodiesel of the invention particularly preferably comprises a primary antioxidant comprising at least one compound having the structure IV.
zo Furthermore, the biodiesel of the invention can comprise a primary antioxidant comprising exclusively compounds selected from among - tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol, - di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2s - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, - tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tent-butyl-2,6-dimethylphenol, 6-tent-butyl-30 2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tert-butylphenol, 4-tent-butylphenol, - di-sec-butylphenols, O.Z. 6496 - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tent-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, - tert-amylphenols, in particular 2-tent-amylphenol, - di-tent-amylphenols, in particular 2,4-di-tert-amylphenol, s - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and/or octadecylphenol, and mixtures of these compounds.
In particular, the biodiesel of the invention comprises C12-CZa fatty acid alkyl esters, preferably to C12-CZa fatty acid methyl esters or C12-CZa fatty acid ethyl esters, which can be present in pure form or as a mixture. In addition, the biodiesel of the invention can further comprise all customary additives such as secondary antioxidants, antifoams. The biodiesel of the invention preferably comprises transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil and/or used cooking oils. The biodiesel of the is invention particularly preferably comprises transesterification products obtained from rapeseed oil, sunflower oil or soybean oil by transesterification. The biodiesel of the invention can also comprise mixtures of transesterification products of various vegetable and/or animal oils.
In addition, the biodiesel of the invention can further comprise all customary additives such as 2o secondary antioxidants, antifoams, low-temperature flow improvers.
Secondary antioxidants which can be present in the biodiesel of the invention are alkylthiomethylphenols, preferably selected from among - 2,4-di((octylthio)methyl)-6-tert-butylphenol, - 2,4-di((octylthio)methyl)-6-methylphenol, 2s - 2,4-di((octylthio)methyl)-6-ethylphenol and - 2,6-di((dodecylthio)methyl)-4-nonylphenol, hydroxylated diphenyl thioethers, preferably selected from among - 2,2'-thiobis[6-tert-butyl-4-methylphenol], - 2,2'-thiobis[4-octylphenol], 30 - 4,4'-thiobis[6-tent-butyl-3-methylphenol], - 4,4'-thiobis[6-tert-butyl-2-methylphenol], - 4,4'-thiobis[3,6-di-sec-amylphenol] and O.Z. 6496 - 4,4'-bis[2,6-dimethyl-4-hydroxyphenyl]disulfide, phosphites or phosphonites, preferably selected from among - triphenyl phosphite, - diphenyl alkyl phosphites, s - phenyl dialkyl phosphites, - tris[nonylphenyl] phosphite, - trilauryl phosphite, - trioctadecyl phosphite, - distearyl pentaeryfhrityl diphosphite, io - tris[2,4-di-tert-butylphenyl] phosphite, - diisodecyl pentaerythrityl diphosphite, - bis[2,4-di-tert-butylphenyl] pentaerythxityl diphosphite, - bis[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite, - bis[isodecyloxy] pentaerythrityl diphosphite, rs - bis[2,4-di-tert-butyl-6-methylphenyl] pentaerythrityl diphosphite, - bis[2,4,6-tri-tent-butylphenyl] pentaerythrityl diphosphite, - tristearyl sorbitol triphosphite, - tetrakis[2,4-di-tert-butylphenyl] 4,4'-biphenylenediphosphonite, - 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, - 6-fluoro-2,4,8,10-tetra-tent-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, - bis[2,4-di-tert-butyl-6-methylphenyl] methyl phosphite and - bis[2,4-di-tert-butyl-6-methylphenyl]ethyl phosphite, or peroxide-destroying compounds, preferably selected from among - esters of (3-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester, 2s - mercaptobenzimidazole, - the zinc salt of 2-mercaptobenzimidazole, - zinc dibutyldithiocarbamate, - dioctadecyl disulfide and - pentaerythrityl tetrakis[[i-dodecylmercapto]propionate, so or mixtures of these compounds.
These secondary antioxidants can be present in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and more preferably from 100 to 8,000 ppm (w/w), in the biodiesel of the invention.
s The biodiesel of the invention is preferably produced using the method of the invention.
The following examples illustrate the method of the invention without restricting the invention to this embodiment.
to Example 1- Production of the samples In a glass beaker, the primary antioxidant is dissolved in biodiesel at 20°C with stirring, and stirring is continued until a clear solution of the primary antioxidant in the biodiesel is obtained. The primary antioxidants used, the biodiesel used and the ratios are shown in Table 1.
is Example 2 - Composition of the primary antioxidants used Primary antioxidant 1 (procured from Degussa AG under the trade mark IONOL 99):
> 99.0% by weight of 2,6-di-tert-butylphenol 20 < 0.5% by weight of 2-tert-butylphenol < 0.5% by weight of 2,4-di-tert-butylphenol Primary antioxidant 2 (procured from Degussa AG under the trade mark IONOL K98):
2s > 98.5% by weight of 6-tert-butyl-2,4-dimethylphenol < 1.5% by weight of 4-tent-butyl-2,6-dimethylphenol and di-tert-butylmethyl-phenols Primary antioxidant 3 30 (procured from Degussa AG under the trade mark IONOL K65):
> 55% by weight of 6-tert-butyl-2,4-dimethylphenol > 15% by weight of 2,6-di-tert-butyl-4-methylphenol 18-22% by weight of tent-butyl-2,5-dimethylphenol < 1 % by weight of 4,6-di-tert-butyl-2-methylphenol < 3.5% by weight of di-tert-butyl-3-methylphenol < 3.5% by weight of 2,5-di-tert-butyl-4-methylphenol s Primary antioxidant 4 (procured from Degussa AG under the trade mark IONOL 75):
> 75% by weight of 2,6-di-tert-butylphenol < 5% by weight of 2-tert-butylphenol io < 0.5% by weight of 4-tert-butylphenol < 3% by weight of 2,4-di-tert-butylphenol < 1 % by weight of 2,5-di-tert-butylphenol < 15.5% by weight of 2,4,6-tri-tent-butylphenol 1 s Example 3 - Testing procedure The oxidation stability of the samples produced as described in Example 1 was examined at a test temperature of 110°C in accordance with the test method DIN EN
14112.
Example 4 - Results of the test method Antioxidant Amount of liquid Oxidation antioxidant stability (in ppm] [in h at 110C]
Rapeseed oil methyl ester - - 5.1 1 500 6.7 2 500 6.5 3 500 6.6 4 500 6.7 Baynox* 2,500 7.1 Used cooking fat methyl ester - - 4.0 1 2,000 9.7 2 2,000 9.5 3 2,000 9.1 4 2, 000 9. 4 Baynox* 10,000 12.0 Soybean oil methyl ester - - 3.6 1 2,000 7.3 2 2,000 6.6 3 2,000 6.3 4 2,000 7.1 Baynox* 10,000 8.8 Sunflower oil methyl ester - - 1.6 1 4,000 8.8 2 4,000 7.8 3 4,000 6.9 4 4,000 8.0 Baynox* 20,000 9.0 O.Z. 6496 * Baynox is an antioxidant from Lanxess and is a solution of the distilled, highly pure active ingredient in biodiesel. The active content has been set to 20% g/1, so that 1 1 of BaynoX
corresponds to 200 g of active ingredient. Analysis showed that the active ingredient in Baynox~ is 2,6-di-tert-butyl-4-hydroxytoluene.
The primary antioxidant used in the method of the invention has a melting point of <- 40°C, preferably <- 39°C
and particularly preferably <- 38°C.
Particularly preferred primary antioxidants include mixtures of:
(1) 2,6-di-tert-butylphenol and other alkylphenols in which the content of 2,6-di-tert-butylphenol is at least 75o by weight, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols in which the content of 6-tert-butyl-2,4-dimethylphenol is at least 75% by weight, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols in which the total content of the first two members is at least 70o by weight.
Secondary antioxidants which can be used in the method of the invention are alkylthiomethylphenols, preferably selected from among 9a - 2,4-di((octylthio)methyl)-6-tert-butylphenol, - 2,4-di((octylthio)methyl)-6-methylphenol, - 2,4-di((octylthio)methyl)-6-ethylphenol and - 2,6-di((dodecylthio)methyl)-4-nonylphenol, s hydroxylated diphenyl thioethers, preferably selected from among - 2,2'-thiobis[6-tert-butyl-4-methylphenol], - 2,2'-thiobis[4-octylphenol], - 4,4'-thiobis[6-tert-butyl-3-methylphenol], - 4,4'-thiobis[6-tert-butyl-2-methylphenol], to - 4,4'-thiobis[3,6-di-sec-amylphenol] and - 4,4'-bas[2,6-dimethyl-4-hydroxyphenyl]disulfide, phosphates or phosphonites, preferably selected from among - triphenyl phosphate, - diphenyl alkyl phosphates, is - phenyl dialkyl phosphates, - tris[nonylphenyl] phosphate, - trilauryl phosphate, - trioctadecyl phosphate, - distearyl pentaerythrityl diphosphite, 20 - tris[2,4-di-tert-butylphenyl] phosphate, diisodecyl pentaerythrityl diphosphite, - bas[2,4-di-tert-butylphenyl] pentaerytlu-ityl diphosphite, - bas[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite, - bas[isodecyloxy] pentaerythrityl diphosphite, O.Z. 6496 - bis[2,4-di-tert-butyl-6-methylphenyl] pentaerythrityl diphosphite, - bis[2,4,6-tri-tent-butylphenyl] pentaerythrityl diphosphite, - tristearyl sorbitol triphosphite, - tetrakis[2,4-di-tert-butylphenyl] 4,4'-biphenylenediphosphonite, s - 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, - 6-fluoro-2,4,8,10-tetra-tent-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, - bis[2,4-di-tert-butyl-6-methylphenyl] methyl phosphite and - bis[2,4-di-tert-butyl-6-methylphenyl] ethyl phosphite, or peroxide-destroying compounds, preferably selected from among - esters of (3-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, - the zinc salt of 2-mercaptobenzimidazole, - zinc dibutyldithiocarbamate, - dioctadecyl disulfide and Is - pentaeryfhrityl tetrakis[(3-dodecylmercapto]propionate, or mixtures of these compounds.
For the purposes of the present invention, the term biodiesel encompasses all the saturated and/or unsaturated alkyl esters of fatty acids, in particular methyl or ethyl esters of fatty acids, 2o which can be used as energy carriers. For the purposes of the present invention, energy carriers include both fuels as sources of heat, for example heating material, and fuels for powering vehicles, for example automobiles, goods vehicles, ships or aircraft. The biodiesel to which the method of the invention is applied is preferably a biodiesel which is usually marketed under the name biodiesel for use as automobile fuel. In particular, the biodiesel to which the method of 2s the invention is applied comprises C12-Cza fatty acid alkyl esters, preferably C12-C2a fatty acid methyl esters or C12-Caa fatty acid ethyl esters, which can be present in pure form or as a mixture. In addition, the biodiesel to which the method of the invention is applied can further comprise all customary additives such as secondary antioxidants, antifoams, low-temperature flow improvers. The method of the invention is preferably applied to biodiesel produced from 3o vegetable and/or animal oils by a process of transesterification with an alcohol, preferably methanol or ethanol, particularly preferably methanol. The method of the invention is more preferably applied to biodiesel comprising transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil, cotton seed oil, peanut oil, maize oil and/or used cooking oils. However, particular preference is given to using biodiesel which is obtained from rapeseed oil, sunflower oil or soybean oil by means of the abovementioned transesterification. The method of the invention can also be applied to mixtures of the trans-s esterification products of various vegetable and/or animal oils.
In a particular embodiment of the method of the invention, mixtures of saturated and/or unsaturated fatty acid alkyl esters with liquid energy carriers, for example mineral diesel fuel or heating oil, can be used as biodiesel. Particular preference is given to using a mixture of to mineral diesel fuel and from 0.1 to 99.9% by volume, in particular from 2 to 10% by volume and preferably from 3 to 5% by volume, of saturated and/or unsaturated fatty acid alkyl esters.
In a subsequent step of the method of the invention, the oxidation-stabilized biodiesel can be added in an amount of from 0.1 to 99.9% by volume, in particular from 1 to 20%
by volume, preferably from 2 to 10% by volume and more preferably from 3 to 5% by volume, to a liquid is energy carrier, in particular mineral diesel fuel or heating oil.
In the method of the invention, the primary antioxidant is preferably added directly, in particular in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and more preferably from 100 to 8,000 ppm (w/w). For the purposes of the present 2o invention, direct addition means that no preparation of a solution or a masterbatch of the primary antioxidant ha.s been carried out in a preceding step. In this step, secondary antioxidants can also be added in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and preferably from 100 to 8,000 ppm (w/w), to the biodiesel.
2s The primary antioxidant is preferably dissolved in the biodiesel with stirnng at a temperature of from 18°C to 60°C, more preferably from 20°C to 40°C.
The invention further provides for the use of a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I for 3o increasing the oxidation stability of biodiesel.
Particular preference is given to using a mixture comprising exclusively compounds having the structure I as primary antioxidant. This mixtur a has the advantage that it comprises exclusively O.Z. 6496 compounds having the structure I which alI have an oxidation-stabilizing action on biodiesel.
Preference is given to using a primary antioxidant comprising at least one compound having the structure II. However, greater preference is given to using a primary antioxidant comprising at least one compound having the structure III. Particular preference is given to s using a primary antioxidant comprising at least one compound having the structure IV.
Furthermore, it is possible to use a primary antioxidant comprising exclusively compounds selected from among - tri-tent-butylphenols, in particular 2,4,6-tri-tent-butylphenol, to - di-tent-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, - tert-butylmethylphenols, in particular 2-tent-butyl-4-methylphenol, 6-tent-butyl-2-1 s methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol, - di-sec-butylphenols, 20 - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, - tert-amylphenols, in particular 2-tert-amylphenol, - di-tent-amylphenols, in particular 2,4-di-tert-amylphenol, - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-Zs dodecylphenol and/or octadecylphenol, and mixtures of these compounds, with this primary antioxidant having a melting point of less than or equal to 40°C.
Pure substances or mixtures which are or comprise compounds having the structures I to IV
3o and have a melting point of greater than 40°C are excluded from the present invention.
The oxidation-stabilized biodiesel of the invention comprises from 10 to 20 000 ppm (w/w), preferably from 50 to 12 000 ppm (w/w) and more preferably from 100 to 8000 ppm (w/w), of O.Z. 6496 a primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I.
The primary antioxidant of the oxidation-stabilized biodiesel of the invention therefore s preferably comprises exclusively alkyphenols and/or substituted alkylphenols. In particular, the oxidation-stabilized biodiesel of the invention comprises a mixture of various substituted and/or unsubstituted alkylphenols as primary antioxidant. The biodiesel of the present invention preferably comprises a primary antioxidant comprising from 0.1 to 99.9% by weight, more preferably from 50 to 99% by weight and particularly preferably from 55 to 99% by io weight, of one or more compounds having the structure I. The biodiesel of the invention particularly preferably comprises a mixture comprising exclusively compounds having the structure I as primary antioxidant.
The biodiesel of the invention preferably comprises a primary antioxidant comprising at least is one compound having the structure II. The biodiesel of the invention more preferably comprises a primary antioxidant comprising at least one compound having the structure III.
The biodiesel of the invention particularly preferably comprises a primary antioxidant comprising at least one compound having the structure IV.
zo Furthermore, the biodiesel of the invention can comprise a primary antioxidant comprising exclusively compounds selected from among - tri-tert-butylphenols, in particular 2,4,6-tri-tert-butylphenol, - di-tert-butylphenols, in particular 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2s - di-tert-butylmethylphenols, in particular 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, - tert-butylmethylphenols, in particular 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, - tert-butyldimethylphenols, in particular 4-tent-butyl-2,6-dimethylphenol, 6-tent-butyl-30 2,4-dimethylphenol, tent-butyl-2,5-dimethylphenol, - tert-butylphenols, in particular 2-tert-butylphenol, 4-tent-butylphenol, - di-sec-butylphenols, O.Z. 6496 - sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tent-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, - tert-amylphenols, in particular 2-tent-amylphenol, - di-tent-amylphenols, in particular 2,4-di-tert-amylphenol, s - 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and/or octadecylphenol, and mixtures of these compounds.
In particular, the biodiesel of the invention comprises C12-CZa fatty acid alkyl esters, preferably to C12-CZa fatty acid methyl esters or C12-CZa fatty acid ethyl esters, which can be present in pure form or as a mixture. In addition, the biodiesel of the invention can further comprise all customary additives such as secondary antioxidants, antifoams. The biodiesel of the invention preferably comprises transesterification products of rapeseed oil, soybean oil, sunflower oil, palm kernel oil, coconut oil, jatropha oil and/or used cooking oils. The biodiesel of the is invention particularly preferably comprises transesterification products obtained from rapeseed oil, sunflower oil or soybean oil by transesterification. The biodiesel of the invention can also comprise mixtures of transesterification products of various vegetable and/or animal oils.
In addition, the biodiesel of the invention can further comprise all customary additives such as 2o secondary antioxidants, antifoams, low-temperature flow improvers.
Secondary antioxidants which can be present in the biodiesel of the invention are alkylthiomethylphenols, preferably selected from among - 2,4-di((octylthio)methyl)-6-tert-butylphenol, - 2,4-di((octylthio)methyl)-6-methylphenol, 2s - 2,4-di((octylthio)methyl)-6-ethylphenol and - 2,6-di((dodecylthio)methyl)-4-nonylphenol, hydroxylated diphenyl thioethers, preferably selected from among - 2,2'-thiobis[6-tert-butyl-4-methylphenol], - 2,2'-thiobis[4-octylphenol], 30 - 4,4'-thiobis[6-tent-butyl-3-methylphenol], - 4,4'-thiobis[6-tert-butyl-2-methylphenol], - 4,4'-thiobis[3,6-di-sec-amylphenol] and O.Z. 6496 - 4,4'-bis[2,6-dimethyl-4-hydroxyphenyl]disulfide, phosphites or phosphonites, preferably selected from among - triphenyl phosphite, - diphenyl alkyl phosphites, s - phenyl dialkyl phosphites, - tris[nonylphenyl] phosphite, - trilauryl phosphite, - trioctadecyl phosphite, - distearyl pentaeryfhrityl diphosphite, io - tris[2,4-di-tert-butylphenyl] phosphite, - diisodecyl pentaerythrityl diphosphite, - bis[2,4-di-tert-butylphenyl] pentaerythxityl diphosphite, - bis[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite, - bis[isodecyloxy] pentaerythrityl diphosphite, rs - bis[2,4-di-tert-butyl-6-methylphenyl] pentaerythrityl diphosphite, - bis[2,4,6-tri-tent-butylphenyl] pentaerythrityl diphosphite, - tristearyl sorbitol triphosphite, - tetrakis[2,4-di-tert-butylphenyl] 4,4'-biphenylenediphosphonite, - 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, - 6-fluoro-2,4,8,10-tetra-tent-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, - bis[2,4-di-tert-butyl-6-methylphenyl] methyl phosphite and - bis[2,4-di-tert-butyl-6-methylphenyl]ethyl phosphite, or peroxide-destroying compounds, preferably selected from among - esters of (3-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester, 2s - mercaptobenzimidazole, - the zinc salt of 2-mercaptobenzimidazole, - zinc dibutyldithiocarbamate, - dioctadecyl disulfide and - pentaerythrityl tetrakis[[i-dodecylmercapto]propionate, so or mixtures of these compounds.
These secondary antioxidants can be present in an amount of from 10 to 20,000 ppm (w/w), preferably from 50 to 12,000 ppm (w/w) and more preferably from 100 to 8,000 ppm (w/w), in the biodiesel of the invention.
s The biodiesel of the invention is preferably produced using the method of the invention.
The following examples illustrate the method of the invention without restricting the invention to this embodiment.
to Example 1- Production of the samples In a glass beaker, the primary antioxidant is dissolved in biodiesel at 20°C with stirring, and stirring is continued until a clear solution of the primary antioxidant in the biodiesel is obtained. The primary antioxidants used, the biodiesel used and the ratios are shown in Table 1.
is Example 2 - Composition of the primary antioxidants used Primary antioxidant 1 (procured from Degussa AG under the trade mark IONOL 99):
> 99.0% by weight of 2,6-di-tert-butylphenol 20 < 0.5% by weight of 2-tert-butylphenol < 0.5% by weight of 2,4-di-tert-butylphenol Primary antioxidant 2 (procured from Degussa AG under the trade mark IONOL K98):
2s > 98.5% by weight of 6-tert-butyl-2,4-dimethylphenol < 1.5% by weight of 4-tent-butyl-2,6-dimethylphenol and di-tert-butylmethyl-phenols Primary antioxidant 3 30 (procured from Degussa AG under the trade mark IONOL K65):
> 55% by weight of 6-tert-butyl-2,4-dimethylphenol > 15% by weight of 2,6-di-tert-butyl-4-methylphenol 18-22% by weight of tent-butyl-2,5-dimethylphenol < 1 % by weight of 4,6-di-tert-butyl-2-methylphenol < 3.5% by weight of di-tert-butyl-3-methylphenol < 3.5% by weight of 2,5-di-tert-butyl-4-methylphenol s Primary antioxidant 4 (procured from Degussa AG under the trade mark IONOL 75):
> 75% by weight of 2,6-di-tert-butylphenol < 5% by weight of 2-tert-butylphenol io < 0.5% by weight of 4-tert-butylphenol < 3% by weight of 2,4-di-tert-butylphenol < 1 % by weight of 2,5-di-tert-butylphenol < 15.5% by weight of 2,4,6-tri-tent-butylphenol 1 s Example 3 - Testing procedure The oxidation stability of the samples produced as described in Example 1 was examined at a test temperature of 110°C in accordance with the test method DIN EN
14112.
Example 4 - Results of the test method Antioxidant Amount of liquid Oxidation antioxidant stability (in ppm] [in h at 110C]
Rapeseed oil methyl ester - - 5.1 1 500 6.7 2 500 6.5 3 500 6.6 4 500 6.7 Baynox* 2,500 7.1 Used cooking fat methyl ester - - 4.0 1 2,000 9.7 2 2,000 9.5 3 2,000 9.1 4 2, 000 9. 4 Baynox* 10,000 12.0 Soybean oil methyl ester - - 3.6 1 2,000 7.3 2 2,000 6.6 3 2,000 6.3 4 2,000 7.1 Baynox* 10,000 8.8 Sunflower oil methyl ester - - 1.6 1 4,000 8.8 2 4,000 7.8 3 4,000 6.9 4 4,000 8.0 Baynox* 20,000 9.0 O.Z. 6496 * Baynox is an antioxidant from Lanxess and is a solution of the distilled, highly pure active ingredient in biodiesel. The active content has been set to 20% g/1, so that 1 1 of BaynoX
corresponds to 200 g of active ingredient. Analysis showed that the active ingredient in Baynox~ is 2,6-di-tert-butyl-4-hydroxytoluene.
Claims (49)
1. A method for increasing the oxidation stability of a biodiesel which comprises:
adding to the biodiesel oil, a primary antioxidant having a melting point of less than or equal to 40°C in an amount of 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C40 alkyl group.
adding to the biodiesel oil, a primary antioxidant having a melting point of less than or equal to 40°C in an amount of 10 to 20,000 ppm (w/w), where the primary antioxidant comprises at least one compound having the structure I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C40 alkyl group.
2. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises one or more compounds having the structure I which is contained in an amount of 0.1 to 99.9% by weight based on the primary antioxidant.
3. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises one or more compounds having the structure I which is contained in an amount of 55 to 90% by weight based on the primary antioxidant.
4. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant consists solely of at least one compound having the structure I.
5. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant is a mixture of those compounds having the structure I, the mixture being selected from the group consisting of those:
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
6. The method as claimed in any one of claims 1 to 4, wherein the primary antioxidant comprises at least 2,6-di-tert-butylphenol having the structure III:
7. The method as claimed in any one of claims 1 to 4, wherein the primary antioxidant comprises at least 6-tert-butyl-2,4-dimethylphenol having the structure IV:
8. The method as claimed in any one of claims 1 to 7, wherein the primary antioxidant has a melting point of less than or equal to 38°C.
9. The method as claimed in any one of claims 1 to 8, wherein the primary antioxidant is added in an amount of 50 to 12,000 ppm (w/w).
10. The method as claimed in any one of claims 1 to 8, wherein the primary antioxidant is added in an amount of 100 to 8,000 ppm (w/w).
11. The method as claimed in any one of claims 1 to 4 and 8 to 10, wherein the primary antioxidant comprises at least one compound selected from the group consisting of a tri-tert-butylphenol, a di-tert-butylphenol, a di-tert-butylmethylphenol, a tert-butylmethylphenol, a tert-butyldimethylphenol, a tert-butylphenol, a di-sec-butylphenol, a sec-butylphenol, a tert-amylphenol, a di-tert-amylphenol.
12. The method as claimed in any one of claims 1 to 4 and 8 to 10, wherein the primary antioxidant comprises at least one compound selected from the group consisting of 2,4,6-tri-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 2-tert-amylphenol, 2,4-di-tert-amylphenol, 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylphenol and octadecylphenol.
13. The method as claimed in any one of claims 1 to 12, which further comprises adding a secondary antioxidant to the biodiesel.
14. The method as claimed in claim 13, wherein the secondary antioxidant is at least one compound selected from the group consisting of an alkylthiomethylphenol, a hydroxylated diphenyl thioether, a phosphate, a phosphonite and a peroxide-destroying compound.
15. The method as claimed in claim 13 or 14, wherein the secondary antioxidant is contained in an amount of 10 to 20,000 ppm (w/w).
16. The method as claimed in claim 13 or 14, wherein the secondary antioxidant is contained in an amount of 50 to 12,000 ppm (w/w).
17. The method as claimed in claim 13 or 14, wherein the secondary antioxidant is contained in an amount of 100 to 8,000 ppm (w/w).
18. The method as claimed in any one of claims 1 to 17, wherein the biodiesel comprises a C12-C24 fatty acid alkyl ester.
19. The method as claimed in claim 18, wherein the fatty acid alkyl ester is a C12-C24 fatty acid methyl ester or a C12-C24 fatty acid ethyl ester.
20. The method as claimed in any one of claims 1 to 19, wherein the biodiesel further comprises a liquid energy carrier.
21. The method as claimed in claim 20, wherein the liquid energy carrier is a mineral diesel fuel or a heating oil.
22. The method as claimed in any one of claims 18 to 21, wherein the fatty acid alkyl ester is contained in an amount of 0.1 to 99.9% by volume based on the biodiesel.
23. The method as claimed in any one of claims 18 to 21, wherein the fatty acid alkyl ester is contained in an amount of 1 to 20% by volume based on the biodiesel.
24. The method as claimed in any one of claims 18 to 21, wherein the fatty acid alkyl ester is contained in an amount of 2 to 10% by volume based on the biodiesel.
25. The method as claimed in any one of claims 18 to 21, wherein the fatty acid alkyl ester is contained in an amount of 3 to 5% by volume based on the biodiesel.
26. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises:
2,6-di-tert-butylphenol contained in an amount of greater than 99.0% by weight;
2-tert-butylphenol contained in an amount of less than 0.5% by weight; and 2,4-di-tert-butylphenol contained in an amount of less than 0.5% by weight, based on the primary antioxidant.
2,6-di-tert-butylphenol contained in an amount of greater than 99.0% by weight;
2-tert-butylphenol contained in an amount of less than 0.5% by weight; and 2,4-di-tert-butylphenol contained in an amount of less than 0.5% by weight, based on the primary antioxidant.
27. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises:
6-tert-butyl-2,4-dimethylphenol contained in an amount of greater than 98.5% by weight; and 4-tert-butyl-2,6-dimethylphenol and a di-tert-butylmethylphenol contained in a combined amount of less than 1.5% by weight, based on the primary antioxidant.
6-tert-butyl-2,4-dimethylphenol contained in an amount of greater than 98.5% by weight; and 4-tert-butyl-2,6-dimethylphenol and a di-tert-butylmethylphenol contained in a combined amount of less than 1.5% by weight, based on the primary antioxidant.
28. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises:
6-tert-butyl-2,4-dimethylphenol contained in an amount of greater than 55% by weight;
2,6-di-tert-butyl-4-methylphenol contained in an amount of greater than 15% by weight;
tert-butyl-2,5-dimethylphenol contained in an amount of 18 to 22% by weight;
4,6-di-tert-butyl-2-methylphenol contained in an amount of less than to by weight;
di-tert-butyl-3-methylphenol contained in an amount of less than 3.5% by weight; and 2,5-di-tert-butyl-4-methylphenol contained in an amount of less than 3.5% by weight, based on the primary antioxidant.
6-tert-butyl-2,4-dimethylphenol contained in an amount of greater than 55% by weight;
2,6-di-tert-butyl-4-methylphenol contained in an amount of greater than 15% by weight;
tert-butyl-2,5-dimethylphenol contained in an amount of 18 to 22% by weight;
4,6-di-tert-butyl-2-methylphenol contained in an amount of less than to by weight;
di-tert-butyl-3-methylphenol contained in an amount of less than 3.5% by weight; and 2,5-di-tert-butyl-4-methylphenol contained in an amount of less than 3.5% by weight, based on the primary antioxidant.
29. The method as claimed in claim 1, wherein the primary antioxidant, without diluting with a solvent, is added to the biodiesel; and wherein the primary antioxidant comprises:
2,6-di-tert-butylphenol contained in an amount of greater than 73% by weight;
2-tert-butylphenol contained in an amount of less than 5% by weight;
4-tert-butylphenol contained in an amount of less than 0.5% by weight;
2,4-di-tert-butylphenol contained in an amount of less than 3% by weight;
2,5-di-tert-butylphenol contained in an amount of less than to by weight; and 2,4,6-tri-tert-butylphenol contained in an amount of less than 15.5% by weight, based on the primary antioxidant.
2,6-di-tert-butylphenol contained in an amount of greater than 73% by weight;
2-tert-butylphenol contained in an amount of less than 5% by weight;
4-tert-butylphenol contained in an amount of less than 0.5% by weight;
2,4-di-tert-butylphenol contained in an amount of less than 3% by weight;
2,5-di-tert-butylphenol contained in an amount of less than to by weight; and 2,4,6-tri-tert-butylphenol contained in an amount of less than 15.5% by weight, based on the primary antioxidant.
30. Use of a primary antioxidant for increasing the oxidation stability of a biodiesel, the primary antioxidant which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C40 alkyl group.
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C40 alkyl group.
31. The use as claimed in claim 30, wherein the primary antioxidant consists solely of at least one compound having the structure I:
32. The use as claimed in claim 30 or 31, wherein the primary antioxidant is a mixture of those compounds having the structure I, the mixture being selected from the group consisting of those:
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
33. The use as claimed in claim 30 or 31, wherein the primary antioxidant comprises at least 2,6-di-tert-butylphenol having the structure III:
34. The use as claimed in claim 30 or 31, wherein the primary antioxidant comprises at least 6-tert-butyl-2,4-dimethylphenol having the structure IV:
35. The use as claimed in any one of claims 30 to 34, wherein the primary antioxidant comprises at least one compound selected from the group consisting of 2,4,6-tri-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 2-tert-amylphenol, 2,4-di-tert-amylphenol, 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylpheonol and octadecylpheonol.
36. An oxidation-stabilized biodiesel oil which comprises:
a biodiesel oil, and a primary antioxidant contained in an amount of 10 to 20,000 ppm (w/w) which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C4o alkyl group.
a biodiesel oil, and a primary antioxidant contained in an amount of 10 to 20,000 ppm (w/w) which has a melting point of less than or equal to 40°C and comprises at least one compound having the structure I
where:
R1 and R2 are the same as or different from each other and are hydrogen, a linear C1-C20 alkyl group or , where * is a carbon atom of the aromatic ring system;
R3 and R5 are the same as or different from each other and are hydrogen or a linear C1-C20 alkyl group; and R4 is hydrogen or a linear C1-C4o alkyl group.
37. The oxidation-stabilized biodiesel oil as claimed in claim 36, wherein the primary antioxidant is contained in an amount of 50 to 12,000 ppm (w/w).
38. The oxidation-stabilized biodiesel oil as claimed in claim 36, wherein the primary antioxidant is contained in an amount of 100 to 8,000 ppm (w/w).
39. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 38, wherein the primary antioxidant comprises one or more compounds having the structure I which is contained in an amount of 0.1 to 99.9%
by weight based on the primary antioxidant.
by weight based on the primary antioxidant.
40. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 38, wherein the primary antioxidant comprises one or more compounds having the structure I which is contained in an amount of 55 to 90% by weight based on the primary antioxidant.
41. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 40, wherein the primary antioxidant is a mixture of those compounds having the structure I, the mixture being selected from the group consisting of those:
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
(1) 2,6-di-tert-butylphenol and other alkylphenols with a content of 2,6-di-tert-butylphenol of at least 75% by weight of the mixture, (2) 6-tert-butyl-2,4-dimethylphenol and other alkylphenols with a content of 6-tert-butyl-2,4-dimethylphenol of at least 75% by weight of the mixture, and (3) 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol and other alkylphenols with a total content of 6-tert-butyl-2,4-dimethylphenol and tert-butyl-2,5-dimethylphenol of at least 70% by weight of the mixture.
42. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 40, wherein the primary antioxidant comprises at least 2,6-di-tert-butylphenol having the structure III:
43. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 40, wherein the primary antioxidant comprises at least 6-tert-butyl-2,4-dimethylphenol having the structure IV:
44. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 43, wherein the primary antioxidant comprises at least one compound selected from the group consisting of 2,4,6-tri-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,6-di-tert-butyl-2-methylphenol, di-tert-butyl-3-methylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2-methylphenol, 4-tert-butyl-2-methylphenol, 6-tert-butyl-3-methylphenol, 4-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-sec-butylphenol, 2-sec-butyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol, 2-tert-amylphenol, 2,4-di-tert-amylphenol, 2-isopropylphenol, 4-octylphenol, 4-nonylphenol, 2,6-di-tert-butyl-4-nonylphenol, 4-dodecylpheonol and octadecylpheonol.
45. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 44, which comprises a C12-C24 fatty acid alkyl ester.
46. The oxidation-stabilized biodiesel oil as claimed in any one of claims 36 to 45, which further comprises a secondary antioxidant which is at least one compound selected from the group consisting of an alkylthiomethylphenol, a hydroxylated diphenyl thioether, a phosphate, a phosphonite and a peroxide-destroying compound.
47. The oxidation-stabilized biodiesel oil as claimed in claim 46, wherein the secondary antioxidant is contained in an amount of 10 to 20,000 ppm (w/w).
48. The oxidation-stabilized biodiesel oil as claimed in claim 46, wherein the secondary antioxidant is contained in an amount of 50 to 12,000 ppm (w/w).
49. The oxidation-stabilized biodiesel oil as claimed in claim 46, wherein the secondary antioxidant is contained in an amount of 100 to 8,000 ppm (w/w).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005015474A DE102005015474A1 (en) | 2005-04-04 | 2005-04-04 | Method for increasing oxidation stability of biodiesel, comprises adding a phenyl compound as primary antioxidant to the biodiesel |
| DE102005015474.3 | 2005-04-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2541591A1 true CA2541591A1 (en) | 2006-10-04 |
Family
ID=36645651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002541591A Abandoned CA2541591A1 (en) | 2005-04-04 | 2006-03-31 | Method of increasing the oxidation stability of biodiesel |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20060218855A1 (en) |
| EP (1) | EP1736528A3 (en) |
| JP (1) | JP2006283028A (en) |
| KR (1) | KR20060106903A (en) |
| CN (1) | CN1847369A (en) |
| AR (1) | AR054335A1 (en) |
| AU (1) | AU2006201342A1 (en) |
| BR (1) | BRPI0601216A (en) |
| CA (1) | CA2541591A1 (en) |
| DE (1) | DE102005015474A1 (en) |
| NZ (1) | NZ546249A (en) |
| SG (1) | SG126070A1 (en) |
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| WO2008065015A1 (en) * | 2006-11-27 | 2008-06-05 | Ciba Holding Inc. | Stabilised biodiesel fuel compositions |
| GB0700534D0 (en) * | 2007-01-11 | 2007-02-21 | Innospec Ltd | Composition |
| US20100107481A1 (en) * | 2007-03-28 | 2010-05-06 | Albemarie Corporation | Antioxidant blends for fatty acid methyl esters (biodiesel) |
| EP2132285A2 (en) * | 2007-04-04 | 2009-12-16 | The Lubrizol Corporation | A synergistic combination of a hindered phenol and nitrogen containing detergent for biodiesel fuel to improve oxidative stability |
| US7918905B2 (en) | 2007-05-17 | 2011-04-05 | Baker Hughes Incorporated | Method for improving biodiesel fuel |
| CN101082004B (en) * | 2007-07-05 | 2010-05-19 | 中国农业科学院油料作物研究所 | Biological diesel modifying agent and preparation method thereof |
| GB0714725D0 (en) | 2007-07-28 | 2007-09-05 | Innospec Ltd | Fuel oil compositions and additives therefor |
| US8430936B2 (en) | 2007-11-30 | 2013-04-30 | Baker Hughes Incorporated | Stabilization of fatty oils and esters with alkyl phenol amine aldehyde condensates |
| WO2009108747A1 (en) * | 2008-02-27 | 2009-09-03 | Wayne State University | The effect of natural and synthetic antioxidants on the oxidative stability of biodiesel |
| CN101619246B (en) * | 2008-06-30 | 2013-11-06 | 中国石油化工股份有限公司 | Diesel composition and application of phenolic amide and/or phenolic ester as antioxidant |
| CN101314730B (en) * | 2008-07-15 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | Supersonic wave auxiliary preparation for anti-oxidant prefabricated solution for biological diesel oil and use method therof |
| CA2734958A1 (en) * | 2008-09-17 | 2010-03-25 | Exxonmobil Research And Engineering Company | Method for improving the oxidation stability of biodiesel as measured by the rancimat test |
| CN101768481B (en) * | 2008-12-29 | 2012-11-14 | 中国石油化工股份有限公司 | Diesel composition |
| CN101768482B (en) * | 2008-12-29 | 2012-11-14 | 中国石油化工股份有限公司 | Diesel composition |
| CN101768483B (en) * | 2008-12-29 | 2013-03-06 | 中国石油化工股份有限公司 | Diesel composition |
| GR1006805B (en) | 2009-02-26 | 2010-06-16 | Dorivale Holdings Limited, | Biodiesel containing non-phenolic additives and thereby possesing enhanced oxidative stability and low acid number. |
| CN101899331B (en) * | 2009-05-27 | 2015-01-14 | 中国石油化工股份有限公司 | Diesel composition and method for improving oxidation stability of biodiesel |
| CN101928614B (en) * | 2009-06-26 | 2013-06-26 | 中国石油化工股份有限公司 | Diesel composite and method for improving oxidation stability of biodiesel |
| ES2749879T3 (en) | 2009-06-26 | 2020-03-24 | China Petroleum & Chem Corp | Diesel composition and process to improve oxidation stability of biodiesel |
| US20120233912A1 (en) * | 2011-03-18 | 2012-09-20 | Otkrytoe Aktsionernoe Obschestvo "Sterlitamaxky Neftekhimichesky Zavod" | Antioxidant additive composition, a solution thereof, and a method for improving the storage stability of biodiesel fuel (variants) |
| EP2597139A1 (en) | 2011-11-24 | 2013-05-29 | LANXESS Deutschland GmbH | Oxidation stabilised biodiesel |
| WO2013076266A1 (en) | 2011-11-24 | 2013-05-30 | Lanxess Deutschland Gmbh | Method for producing oxidation-stabilised biodiesel |
| EP2896682A1 (en) | 2014-01-17 | 2015-07-22 | LANXESS Deutschland GmbH | Biodiesel stabilised against oxidation |
| CN112755585A (en) * | 2020-12-22 | 2021-05-07 | 北京元泰达环保科技有限公司 | Antioxidant production method |
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| US2275175A (en) * | 1939-11-30 | 1942-03-03 | Standard Oil Dev Co | Motor fuel |
| GB753794A (en) * | 1953-10-07 | 1956-08-01 | Universal Oil Prod Co | Improvements in or relating to antioxidant compositions and food products stabilizedtherewith |
| NL99615C (en) * | 1955-05-18 | |||
| US3166509A (en) * | 1963-01-09 | 1965-01-19 | Ethyl Corp | Antioxidant composition |
| FR1530056A (en) * | 1967-06-30 | 1968-06-21 | Ethyl Corp | Jet engine fuels |
| DE3500938A1 (en) | 1985-01-14 | 1986-07-17 | Henkel KGaA, 4000 Düsseldorf | STABILIZATION OF PALM CORE OIL AND PALM CORE FATTY ACID ALKYL ESTERS FOR THEIR PROCESSING TO COLOR-NEUTRAL REACTION PRODUCTS |
| TW276260B (en) * | 1992-07-15 | 1996-05-21 | Ciba Geigy Ag | |
| AU674052B2 (en) * | 1993-05-24 | 1996-12-05 | Lubrizol Corporation, The | Pour point depressant treated fatty acid esters as biodegradable, combustion engine fuels |
| US5578090A (en) * | 1995-06-07 | 1996-11-26 | Bri | Biodiesel fuel |
| US5891203A (en) * | 1998-01-20 | 1999-04-06 | Ethyl Corporation | Fuel lubricity from blends of a diethanolamine derivative and biodiesel |
| US6475252B1 (en) * | 1998-09-17 | 2002-11-05 | University Of Dayton | Stabilizing additive for the prevention of oxidation and peroxide formation |
| US6740508B2 (en) * | 1999-02-11 | 2004-05-25 | Renessen Llc | Fermentation-based products from corn and method |
| US7208022B2 (en) * | 2002-03-14 | 2007-04-24 | The Lubrizol Corporation | Ethanol-diesel fuel composition and methods thereof |
| AU2003221899B2 (en) * | 2002-04-23 | 2008-11-27 | The Lubrizol Corporation | Method of operating internal combustion engine by introducing antioxidant into combustion chamber |
| US6923838B2 (en) * | 2002-05-23 | 2005-08-02 | Advanced Combustion Technologies, Inc. | Fuel additive composition and method for treatment of middle distillate fuels and gasoline |
| DE10252714B4 (en) | 2002-11-13 | 2007-09-13 | Lanxess Deutschland Gmbh | Method for increasing the oxidation stability of biodiesel and the use of mono- or dialkylhydroxytoluene to increase the oxidation stability of biodiesel |
| DE10252715A1 (en) | 2002-11-13 | 2004-05-27 | Bayer Ag | Process for the improving the storage stability of biodiesel comprises addition of 2,4-di-tert-butylhydroxy toluene |
| EP1972679B1 (en) | 2002-11-13 | 2017-05-10 | LANXESS Deutschland GmbH | Use of 2,6-di-tert.-butyl-p-kresol to increase the storage stability of biodiesel |
| AU2004200235B2 (en) * | 2003-01-31 | 2009-12-03 | Chevron U.S.A. Inc. | Stable olefinic, low sulfur diesel fuels |
-
2005
- 2005-04-04 DE DE102005015474A patent/DE102005015474A1/en not_active Withdrawn
-
2006
- 2006-02-10 EP EP06101504A patent/EP1736528A3/en not_active Withdrawn
- 2006-03-10 SG SG200601627A patent/SG126070A1/en unknown
- 2006-03-21 US US11/384,241 patent/US20060218855A1/en not_active Abandoned
- 2006-03-29 AR ARP060101221A patent/AR054335A1/en unknown
- 2006-03-30 AU AU2006201342A patent/AU2006201342A1/en not_active Abandoned
- 2006-03-30 NZ NZ546249A patent/NZ546249A/en unknown
- 2006-03-31 CA CA002541591A patent/CA2541591A1/en not_active Abandoned
- 2006-03-31 JP JP2006098322A patent/JP2006283028A/en not_active Withdrawn
- 2006-04-03 CN CNA2006100719299A patent/CN1847369A/en active Pending
- 2006-04-04 BR BRPI0601216-7A patent/BRPI0601216A/en not_active IP Right Cessation
- 2006-04-04 KR KR1020060030620A patent/KR20060106903A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP1736528A2 (en) | 2006-12-27 |
| DE102005015474A1 (en) | 2006-10-05 |
| NZ546249A (en) | 2007-08-31 |
| JP2006283028A (en) | 2006-10-19 |
| BRPI0601216A (en) | 2006-12-05 |
| AR054335A1 (en) | 2007-06-20 |
| US20060218855A1 (en) | 2006-10-05 |
| CN1847369A (en) | 2006-10-18 |
| AU2006201342A1 (en) | 2006-10-19 |
| SG126070A1 (en) | 2006-10-30 |
| EP1736528A3 (en) | 2007-01-10 |
| KR20060106903A (en) | 2006-10-12 |
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