NZ546249A - Method of increasing the oxidation stability of biodiesel using antioxidants based on substituted alkylphenol - Google Patents
Method of increasing the oxidation stability of biodiesel using antioxidants based on substituted alkylphenolInfo
- Publication number
- NZ546249A NZ546249A NZ546249A NZ54624906A NZ546249A NZ 546249 A NZ546249 A NZ 546249A NZ 546249 A NZ546249 A NZ 546249A NZ 54624906 A NZ54624906 A NZ 54624906A NZ 546249 A NZ546249 A NZ 546249A
- Authority
- NZ
- New Zealand
- Prior art keywords
- biodiesel
- tert
- hydrogen
- alkyl group
- carbon atoms
- Prior art date
Links
- 239000003225 biodiesel Substances 0.000 title claims abstract description 92
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 26
- 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 14
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 150000001721 carbon Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 12
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 9
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 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 description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 6
- 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
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000002600 sunflower oil Substances 0.000 description 6
- 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 description 5
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 150000004702 methyl esters Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- 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 description 4
- 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 description 4
- 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 description 4
- 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 description 4
- 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 description 4
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 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 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-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
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- BRIRGRNYHFFFHD-UHFFFAOYSA-N 2,3-bis(2-methylbutan-2-yl)phenol Chemical class CCC(C)(C)C1=CC=CC(O)=C1C(C)(C)CC BRIRGRNYHFFFHD-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 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 description 3
- 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 description 3
- BGRKGHSKCFAPCL-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC=C1O BGRKGHSKCFAPCL-UHFFFAOYSA-N 0.000 description 3
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 3
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 3
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-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
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N ortho-isopropyl phenol Natural products CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 3
- 239000003346 palm kernel oil Substances 0.000 description 3
- 235000019865 palm kernel oil Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 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
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- ROOPEIGRBDVOKP-UHFFFAOYSA-N 2,3-di(butan-2-yl)phenol Chemical class CCC(C)C1=CC=CC(O)=C1C(C)CC ROOPEIGRBDVOKP-UHFFFAOYSA-N 0.000 description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 2
- SDNVJMZXSOXXQN-UHFFFAOYSA-N 3,4-ditert-butyl-2-methylphenol Chemical class CC1=C(O)C=CC(C(C)(C)C)=C1C(C)(C)C SDNVJMZXSOXXQN-UHFFFAOYSA-N 0.000 description 2
- OXPSEZLCVXHNQE-UHFFFAOYSA-N 4-tert-butyl-2,3-dimethylphenol Chemical class CC1=C(C)C(C(C)(C)C)=CC=C1O OXPSEZLCVXHNQE-UHFFFAOYSA-N 0.000 description 2
- 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 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
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-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
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 235000015073 liquid stocks Nutrition 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 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
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 2
- 239000003981 vehicle Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 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
- JJULABXIXFRDCQ-UHFFFAOYSA-N 2,3,4-tritert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C JJULABXIXFRDCQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- 125000004429 atom Chemical group 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—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
-
- 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
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- 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
-
- 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
-
- 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
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Abstract
A method of increasing the oxidation stability of biodiesel is disclosed, which comprises adding a primary antioxidant having a melting point of less than or equal to 40 Deg C to the biodiesel to be stabilized in an amount of from 10 to 20000 ppm (w/w), where the primary antioxidant comprises at least one antioxidant based on substituted alkylphenol compounds of formula (I) where: R1 and R2 are hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or as defined in the specification; R3 and R5 are hydrogen or a linear alkyl group having from 1 to 20 carbon atoms; R4 is hydrogen or a linear alkyl group having from 1 to 40 carbon atoms; where both the substituents of the type R1 and R2 and those of the type R3 and R5 are in each case identical or different.
Description
New Zealand Paient Spedficaiion for Paient Number 546249
4 6 2 4 9
*10051094849*
PATENTS FORM NO. 5
Our ref: JC225519NZPR
NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION
Method of increasing the oxidation stability of biodiesel
We, Degussa AG a German company of Bennigsenplatz 1, D-40474 Dusseldorf, The Federal Republic of Germany hereby declare the invention, for which we pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement:
intellectual property office of n.z.
MAR 2006
RECEIVED
100766935_1 .DOC: JC:qwgtn
(followed by page 1a)
O.Z. 6496
1 a
Method of increasing the oxidation stability of biodiesel
The invention relates to a method of increasing the oxidation stability of biodiesel.
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 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.
Since the importance of biodiesel as an alternative diesel fuel for passenger cars has been continually increasing in importance 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 (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 the 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.
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-tert-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 to 2% by weight of monoalkylhydroxytoluene or dialkylhydroxytoluene, based on the total solution in biodiesel.
O.Z. 6496
2
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 5 biodiesel.
It is an object of the present invention to provide an improved method of increasing the oxidation stability of biodiesel, or to at least provide a useful alternative. 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 use of primary antioxidants in biodiesel, or to at least provide a useful alternative.
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 15 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 primaiy antioxidant can, in the method of the invention, be mixed as liquid directly into the biodiesel without this primary antioxidant firstly 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 20 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 30 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 primaiy antioxidants according to the prior art, since the liquid generally contains only
O.Z. 6496
3
about 20% 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
Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or
*, where * is a carbon atom of the aromatic ring system,
R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms,
where both the substituents of the type Rj and R2 and those of the type R3 and R5 are in each case identical or different.
oh where:
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
O.Z. 6496
4
oh
R4 R
where:
Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or
*, where * is a carbon atom of the aromatic ring system,
R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms,
where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different, for increasing the oxidation stability of biodiesel.
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
Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or
R
OH
where:
*, where * is a caibon atom of the aromatic ring system, R3, Rs = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms,
O.Z. 6496
where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different.
The inventive method of increasing the oxidation stability of biodiesel comprises adding a primary antioxidant having a melting point or 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
Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or
*, whore * is a carbon atom of the aromatic ring system,
R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms,
where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different.
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.
oh where:
1. Chain initiation
O.Z. 6496
6
R H
R" +
r h + 02
>■ R" + H02
2. Chain propagation
R" + 02
R02"
ROz- + R' H
^ ROOH + R'•
3. Chain termination
R02- + AOH
ROOH + AO'
AO ' + R"
-a- 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 caibon-hydrogen bond which is located in the allyl position relative to the double bond is 10 preferentially attacked by the oxygen:
The primaiy 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 15 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 20 antioxidant in the method of the invention.
H
H
O.Z. 6496
7
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
Ri, R2 = hydrogen, a linear alkyl group having from 1 to 4 carbon atoms or
*, where * is a carbon atom of the aromatic ring system,
R3, R5 = hydrogen, a linear alkyl group having from 1 to 4 carbon atoms,
R4 = hydrogen, a linear alkyl group having from 1 to 4 carbon atoms,
where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different.
Preference is given to adding a primary antioxidant comprising at least one compound having the structure III
OH
II
where:
OH
m to the biodiesel in the method of the invention.
O.Z. 6496
8
Particular preference is given to adding a primary antioxidant comprising at least one compound having the structure IV
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
- 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,
- 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-dimethylpheQol, tert-butyl-2,5-dimethylphenol,
- tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol, di-sec-butylphenols,
- 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-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
- 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.
OH
CH3
IV
O.Z.6496
9
Pure substances or mixtures which are or comprise compounds having the structures 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.
Secondary antioxidants which can be used in the method of the invention are alkylthiomethylphenols, preferably selected from among
- 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,
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],
- 4,4'-thiobis[3,6-di-sec-amylphenol] and
- 4,4' -bis[2,6-dimethyl-4-hydroxyphenyl]disulfide,
phosphites or phosphonites, preferably selected from among
- triphenyl phosphite,
- diphenyl alkyl phosphites,
- phenyl dialkyl phosphites,
- tris[nonylphenyl] phosphite,
- trilauiyl phosphite,
- trioctadecyl phosphite,
- distearyl pentaerythrityl diphosphite,
- tris[2,4-di-tert-butylphenyl] phosphite,
- diisodecyl pentaerythrityl diphosphite,
- bis[2,4-di-tert-butylphenyl] pentaerythrityl diphosphite,
- bis[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite,
- bis[isodecyloxy] pentaerythrityl diphosphite,
O.Z. 6496
- bis[2,4-di-tert-butyl-6-metbylphenyl] pentaerythrityl diphosphite,
- bis[2,4,6-tri-tert-butylphenyl] pentaerythrityl diphosphite,
- tristearyl sorbitol triphosphite,
- tetrakis[2,4-di-tert-buiylphenyl] 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-tert-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 p-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester,
- mercaptobenzimidazole,
- the zinc salt of 2-mercaptobenzimidazole,
- zinc dibutyldithiocarbamate,
- dioctadecyl disulfide and
- pentaerythrityl tetrakis[P-dodecylmercapto]propionate,
or mixtures of these compounds.
t
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, 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 the invention is applied comprises C12-C24 fatty acid alkyl esters, preferably C12-C24 fatty acid methyl esters or C12-C24 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 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
O.Z. 6496
11
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 transesterification 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 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% volume, to a liquid 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 8000 ppm (w/w). For the purposes of the present invention, direct addition means that no preparation of a solution or a masterbatch of the primary antioxidant has 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 8000 ppm (w/w), to the biodiesel.
The primary antioxidant is preferably dissolved in the biodiesel with stirring 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 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 mixture has the advantage that it comprises exclusively
O.Z. 6496
12
compounds having the structure I which all 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 HI. Particular preference is given to 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-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,
- 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, tert-butyl-2,5-dimethylphenol,
- tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol,
- di-sec-butylphenols,
- sec-butylphenols, in particular 2-sec-butylphenol, 2-seobutyl-4-tert-butylphenol, 4-sec-butyl-2,6-di-tert-butylphenol,
- tert-amylphenols, in particular 2-tert-amylphenol,
di-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
- 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 primaiy 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 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
13
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 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 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 one compound having the structure EL The biodiesel of the invention more preferably comprises a primary antioxidant comprising at least one compound having the structure in. The biodiesel of the invention particularly preferably comprises a primary antioxidant comprising at least one compound having the structure IV.
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,
- 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-tert-butyl-2,6-dimethylphenol, 6-tert-butyl-2,4-dimethylphenol, tert-butyl-2,5-dimethylphenol,
- tert-butylphenols, in particular 2-tert-butylphenol, 4-tert-butylphenol, di-sec-butylphenols,
O.Z. 6496
14
sec-butylphenols, in particular 2-sec-butylphenol, 2-sec-butyl-4-tert-butylpbenol, 4-sec-
butyl-2,6-di-tert-butylphenol,
tert-axnylphenols, in particular 2-tert-amylphenol,
di-tert-amylphenols, in particular 2,4-di-tert-amylphenol,
- 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-C24 fatty acid alkyl esters, preferably C12-C24 fatty acid methyl esters or C12-C24 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 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 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-methylpheQol,
- 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],
- 4,4'-thiobis[6-tert-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,
- phenyl dialkyl phosphites,
- tris[nonylphenyl] phosphite,
- trilauryl phosphite,
- trioctadecyl phosphite,
- distearyl pentaerythrityl diphosphite,
- tris[2,4-di-tert-butylphenyl] phosphite,
- diisodecyl pentaerythrityl diphosphite,
- bis[2,4-di-tert-butylphenyl] pentaerythrityl diphosphite,
- bis[2,6-di-tert-butyl-4-methylphenyl] pentaerythrityl diphosphite,
- bis[isodecyloxy] pentaerythrityl diphosphite,
- bis[2,4-di-tert-butyl-6-methylphenyl] pentaerythrityl diphosphite,
- bis[2,4,6-tri-tert-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]-l,3,2-dioxaphosphocine,
- 6-fluoro-2,4,8,10-tetra-tert-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 p-thiodipropionic acid, preferably the lauryl, stearyl, myristyl or tridecyl ester,
- mercaptobenzimidazole,
- the zinc salt of 2-mercaptobenzimidazole,
- zinc dibutyldithiocarbamate,
- dioctadecyl disulfide and
- pentaerythrityl tetrakis[p-dodecylmercapto]propionate,
or mixtures of these compounds.
O.Z. 6496
16
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 8000 ppm (w/w), in the biodiesel of the invention.
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.
Example 1 - Production of the samples
In a glass beaker, the primaiy 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.
Example 2 - Composition of the primary antioxidants used Primary antioxidant 1
(procured from Degussa AG under the trade name IONOL 99):
> 99.0% by weight of 2,6-di-tert-butylphenol
< 0.5% by weight of 2-tert-butylphenol
< 0.5% by weight of 2,4-di-tert-butylphenol
Primaiy antioxidant 2
(procured from Degussa AG under the trade name IONOL K98):
> 98.5% by weight of 6-tert-butyl-2,4-diinethylphenol
< 1.5% by weight of 4-tert-butyl-2,6-dimethylphenol and di-tert-butylmethyl-phenols
Primary antioxidant 3
(procured from Degussa AG under the trade name 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 tert-butyl-2,5-dimethylphenol
O.Z. 6496
17
< 1% by weight
< 3.5% by weight
< 3.5% by weight of 4,6-di-tert-butyl-2-methylphenol of di-tert-butyl-3 -methylphenol of 2,5-di-tert-butyl-4-methylphenol
Primary antioxidant 4
(procured from Degussa AG under the trade name IONOL 75): > 75% by weight of 2,6-di-tert-butylphenol of 2-tert-butylphenol of 4-tert-butylphenol of 2,4-di-tert-butylphenol of 2,5-di-tert-butylphenol
< 5% by weight
< 0.5% by weight
< 3% by weight
< 1% by weight
< 15.5% by weight of 2,4,6-tri-tert-butylphenol
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.
O.Z. 6496
18
Example 4 - Results of the test method intellectual property office of n.z.
i -3 APR 2KB RECEIVED
Antioxidant
Amount of liquid antioxidant fin ppm J
Oxidation stability fin h at 110°C]
Rapeseed oil methyl ester
-
-
.1
1
500
6.7
2
500
6.5
3
500
6.6
4
500
6.7
Baynox *
2500
7.1
Used cooking fat methyl ester
-
-
4.0
1
2000
9.7
2
2000
9.5
3
2000
9.1
4
2000
9.4 .
Baynox *
000
12.0
Soybean oil methyl ester
-
-
3.6
1
2000
7.3
2
2000
6.6
3
2000
6.3
4
2000
7.1
Baynox *
000
8.8
Sunflower oil methyl ester
-
-
1.6
1
4000
8.8
2
4000
7.8
3
4000
6.9
4
4000
8.0
Baynox*
000
9.0
Claims (8)
1. 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 where: Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or *, where * is a carbon atom of the aromatic ring system, R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms, where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different
2. The method as claimed in claim 1, wherein a mixture comprising from 0.1 to 99.9% by weight of one or more compounds having the structure I is used as primary antioxidant.
3. The method as claimed in claim 1, wherein a mixture comprising exclusively compounds having the structure I is used as primary antioxidant. OH O.Z. 6496 21
4. The method as claimed in at least one of claims 1 to 3, wherein the primary antioxidant comprises at least one compound having the structure h3c. h,c in.
5. The method as claimed in at least one of claims 1 to 3, wherein the primary antioxidant comprises at least one compound having the structure 10 h,c. hIC ch oh ch, ch, IV.
6. 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 oh ri 15 2 I where: O.Z. 6496 22 Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or *, where * is a carbon atom of the aromatic ring system, R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms, where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different, for increasing the oxidation stability of biodiesel.
7. 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 Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or *, where * is a carbon atom of the aromatic ring system, R3, Rs = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms, where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different oh where:
8. A method as claimed in any one of claims 1 to 5 substantially as herein described with reference to Examples 1 to 4. 23 An oxidation stabilised biodiesel as claimed in claim 7 substantially as herein described with reference to Examples 1 to 4. Degussa AG O.Z. 6496 5*624 9 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 Ri, R2 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms or *, where * is a carbon atom of the aromatic ring system, R3, R5 = hydrogen, a linear alkyl group having from 1 to 20 carbon atoms, R4 = hydrogen, a linear alkyl group having from 1 to 40 carbon atoms, where both the substituents of the type Ri and R2 and those of the type R3 and R5 are in each case identical or different OH where: INTELLECTUAL PROPERTY OFFICE OF N.Z. 30 MAR 2006 received
Applications Claiming Priority (1)
| 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NZ546249A true NZ546249A (en) | 2007-08-31 |
Family
ID=36645651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NZ546249A NZ546249A (en) | 2005-04-04 | 2006-03-30 | Method of increasing the oxidation stability of biodiesel using antioxidants based on substituted alkylphenol |
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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| CA2670065A1 (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 |
| CA2681753A1 (en) * | 2007-03-28 | 2008-10-09 | Albemarle Corporation | Antioxidant blends for fatty acid methyl esters (biodiesel) |
| CA2681312C (en) * | 2007-04-04 | 2015-10-27 | 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 |
| EP2342311B1 (en) * | 2008-09-17 | 2016-03-09 | 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 |
| US20120124896A1 (en) | 2009-06-26 | 2012-05-24 | Research Institute Of Petroleum Processing, Sinopec | Diesel Composition and Method of Increasing Biodiesel Oxidation Stability |
| 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 |
| 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) |
| WO2013076266A1 (en) | 2011-11-24 | 2013-05-30 | Lanxess Deutschland Gmbh | Method for producing oxidation-stabilised biodiesel |
| EP2597139A1 (en) | 2011-11-24 | 2013-05-29 | LANXESS Deutschland GmbH | 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 |
| EP1499700A1 (en) * | 2002-04-23 | 2005-01-26 | The Lubrizol Corporation | Method of operating internal combustion engine by introducing antioxidant into combustion chamber |
| WO2003099967A2 (en) * | 2002-05-23 | 2003-12-04 | Maubert Paul H | Fuel additive composition and method for treatment of middle distillate fuels and gasoline |
| PL203138B1 (en) | 2002-11-13 | 2009-08-31 | Lanxess Deutschland Gmbh | Use of 2,4-di-tert.-butylhydroxytoluene for increasing the storage stability of bio-diesel |
| 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 |
| DE20221700U1 (en) * | 2002-11-13 | 2007-03-15 | Lanxess Deutschland Gmbh | Oxidation-stabilized 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 NZ NZ546249A patent/NZ546249A/en unknown
- 2006-03-30 AU AU2006201342A patent/AU2006201342A1/en not_active Abandoned
- 2006-03-31 JP JP2006098322A patent/JP2006283028A/en not_active Withdrawn
- 2006-03-31 CA CA002541591A patent/CA2541591A1/en not_active Abandoned
- 2006-04-03 CN CNA2006100719299A patent/CN1847369A/en active Pending
- 2006-04-04 KR KR1020060030620A patent/KR20060106903A/en not_active Application Discontinuation
- 2006-04-04 BR BRPI0601216-7A patent/BRPI0601216A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1847369A (en) | 2006-10-18 |
| BRPI0601216A (en) | 2006-12-05 |
| JP2006283028A (en) | 2006-10-19 |
| DE102005015474A1 (en) | 2006-10-05 |
| CA2541591A1 (en) | 2006-10-04 |
| EP1736528A2 (en) | 2006-12-27 |
| US20060218855A1 (en) | 2006-10-05 |
| KR20060106903A (en) | 2006-10-12 |
| SG126070A1 (en) | 2006-10-30 |
| AU2006201342A1 (en) | 2006-10-19 |
| AR054335A1 (en) | 2007-06-20 |
| EP1736528A3 (en) | 2007-01-10 |
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