CN1847369A - Method of increasing the oxidation stability of biodiesel - Google Patents
Method of increasing the oxidation stability of biodiesel Download PDFInfo
- Publication number
- CN1847369A CN1847369A CNA2006100719299A CN200610071929A CN1847369A CN 1847369 A CN1847369 A CN 1847369A CN A2006100719299 A CNA2006100719299 A CN A2006100719299A CN 200610071929 A CN200610071929 A CN 200610071929A CN 1847369 A CN1847369 A CN 1847369A
- Authority
- CN
- China
- Prior art keywords
- oxidant
- biofuel
- main anti
- sub
- carbon atom
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title abstract description 3
- 238000007254 oxidation reaction Methods 0.000 title abstract description 3
- 239000003225 biodiesel Substances 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 16
- 239000003963 antioxidant agent Substances 0.000 claims description 85
- 235000006708 antioxidants Nutrition 0.000 claims description 85
- 230000003078 antioxidant effect Effects 0.000 claims description 84
- 239000002551 biofuel Substances 0.000 claims description 83
- 239000000203 mixture Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- 230000003064 anti-oxidating effect Effects 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- -1 unsaturated fatty acid ester Chemical class 0.000 description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 229960003742 phenol Drugs 0.000 description 22
- 150000001721 carbon Chemical group 0.000 description 21
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 229940059574 pentaerithrityl Drugs 0.000 description 14
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- 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 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 150000004702 methyl esters Chemical class 0.000 description 7
- WPIHPTFPTAQLFR-UHFFFAOYSA-N 1-butyl-2-methylbenzene phenol Chemical group C1(=CC=CC=C1)O.CC1=C(C=CC=C1)CCCC WPIHPTFPTAQLFR-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
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019486 Sunflower oil Nutrition 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 6
- 239000002600 sunflower oil Substances 0.000 description 6
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical group CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 5
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-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
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229960004217 benzyl alcohol Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical group CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 3
- BDHVDYUIWOIODW-UHFFFAOYSA-N 2-butyl-4-nonylphenol Chemical group CCCCCCCCCC1=CC=C(O)C(CCCC)=C1 BDHVDYUIWOIODW-UHFFFAOYSA-N 0.000 description 3
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical group CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 3
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-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
- 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 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 group CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 3
- 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 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
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 239000008162 cooking oil Substances 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000010773 plant oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 2
- ZGVRHXWPSIEOMJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)tridecane-1,3-diol Chemical compound C(CCCCCCCCC)C(O)C(CO)(CO)CO ZGVRHXWPSIEOMJ-UHFFFAOYSA-N 0.000 description 2
- OKLNGCVEHOKJIY-UHFFFAOYSA-N 3-butyl-4-methylphenol Chemical group CCCCC1=CC(O)=CC=C1C OKLNGCVEHOKJIY-UHFFFAOYSA-N 0.000 description 2
- BCZQMWDTKGBZFG-UHFFFAOYSA-N 4-[(4-hydroxy-2,6-dimethylphenyl)disulfanyl]-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1SSC1=C(C)C=C(O)C=C1C BCZQMWDTKGBZFG-UHFFFAOYSA-N 0.000 description 2
- IWQLLQOHIQCMGR-UHFFFAOYSA-N 4-butyl-5H-benzo[d][1,3,2]benzodioxaphosphocine Chemical group C(CCC)C1=CC=CC=2OPOC3=C(CC21)C=CC=C3 IWQLLQOHIQCMGR-UHFFFAOYSA-N 0.000 description 2
- YHOKOCFZNYBCKX-UHFFFAOYSA-N C(CCCCCCCCCCC)P(O)(O)O Chemical class C(CCCCCCCCCCC)P(O)(O)O YHOKOCFZNYBCKX-UHFFFAOYSA-N 0.000 description 2
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical class CP(O)(O)O GFMYEVPBEJFZHH-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
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 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
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 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
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 210000000582 semen Anatomy 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
- 239000000126 substance Substances 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 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
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical class CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 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
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical group C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 235000013311 vegetables 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Combustion & Propulsion (AREA)
- Aviation & Aerospace Engineering (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Lubricants (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses an oxidation stability increasing method of biological diesel, which adds 10-20000ppm (w/w) main anti-oxidizing agent with fusing point not more than 40 deg.c in the biological diesel, wherein the main anti-oxidizing agent contains at least one compound with structure I; R<SUB>1</SUB>, R<SUB>2</SUB> equals hydrogen, straight chain alkyl group with 1-20 carbon atoms (* is carbon atom of aromatic system); R<SUB>3</SUB>, R<SUB>5</SUB> equals hydrogen, straight chain alkyl group with 1-20 carbon atoms; R<SUB>4</SUB> equals hydrogen, straight chain alkyl group with 1-40 carbon atoms; the substituted group and type of R<SUB>1</SUB> and R<SUB>2</SUB> is the same with or different from R<SUB>3</SUB> and R<SUB>5</SUB> 's under each condition.
Description
Technical field
The present invention relates to increase the method for the oxidative stability of biofuel.
Background technology
Be biofuel (biodiesel) in a kind of substitute of the ever-increasing conventional diesel oil fuel of usage degree just now, it comprises the mono alkyl ester of vegetables oil, animal tallow and used fat for cooking.Biofuel obtains with the transesterification of alcohol in the presence of catalyzer as rapeseed oil, soybean oil or sunflower oil and used cooking oil by oil.
Recently, because biofuel is just becoming more and more important as the available diesel oil fuel of passenger vehicle, so obtain very high concern about the production of biofuel is same recent years.Biofuel has high-load unsaturated fatty acid ester, and it can be easy to the oxidation by airborne oxygen institute.The product that makes (comprising acid, resin) may cause corrosion and block in squirt pump and/or oil pipe.Constantly increase and use alternative biofuel to cause the oxidation-stabilized biofuel of needs as automobile fuel.According to prior art, preferably in this biofuel, add 2,6-two-tertiary butyl-4-methylphenol (BHT) as main anti-oxidant so that satisfy the oxidation-stabilized sexual needs of standard DIN EN 14214.
2,6-two-tertiary butyl-4-methylphenol is described in the European patent EP 0 189 049 as the purposes of antioxidant.At this, having described quantity is 2 of 10-100ppm, and 6-two-tertiary butyl-4-methylphenol has in the palmitic methyl esters of 12-18 carbon atom the purposes as unique stablizer in lipid acid.
DE 102 52 714 and WO 2004/044104 have also described a kind of by adding 2, and 6-two-tertiary butyl-4-hydroxy toluene increases the method for biofuel oxidative stability.The liquid storage liquid that will be dissolved in monoalkyl hydroxytoluene that contains 15-60% weight in the biofuel or dialkyl group hydroxytoluene joins to be treated in the stable biofuel, based on the total solution in the biofuel, obtaining concentration is the monoalkyl hydroxytoluene or the dialkyl group hydroxytoluene of 0.005-2% weight.
DE 102 52 715 has described a kind of method that increases storage stability of bio-diesel, wherein will be dissolved in and contain 2 of 15-60% weight in the biofuel, the liquid storage liquid of 4-two-tertiary butyl hydroxytoluene joins to be treated in the stable biofuel, based on the total solution in the biofuel, obtaining concentration is 2 of 0.005-2% weight, 4-two-tertiary butyl hydroxytoluene.
Summary of the invention
An object of the present invention is to provide improving one's methods of a kind of oxidative stability that increases biofuel.Especially, the processing characteristics that an object of the present invention is to improve main anti-oxidant in the biofuel is also improved economy or the purposes of main anti-oxidant in biofuel thus.
Now find surprisingly, in biofuel, add liquid main anti-oxidant, might improve the processing characteristics of main anti-oxidant in biofuel based on the substituted alkyl phenol of structure I.The main anti-oxidant of Shi Yonging has low fusing point in the methods of the invention, and promptly fusing point is less than or equal to 40 ℃.Because its fusing point is low, in the method for the invention, this main anti-oxidant can be used as liquid and directly is blended in the biofuel, does not need this main anti-oxidant at first must be dissolved in solvent as alcohol or be dissolved in the biofuel.Therefore, the preparation of the masterbatch of this main anti-oxidant in biofuel can be save.This masterbatch uses the stand-by biofuel of this masterbatch to be prepared usually.In the remote situation of distance between biofuel and antioxidant manufacturers, especially, in the situation of the main anti-oxidant of prior art, it is expensive that this will cause storing and transport.Therefore, the main anti-oxidant of Shi Yonging causes the lower production cost of oxidation-stabilized biofuel in the methods of the invention, because, at first, containing the solution of active ingredient main anti-oxidant or the preparation of masterbatch just can be save, secondly, method of the present invention shows: the product mixture from the manufacturing processed of substituted alkyl phenol can not need complicated separation and purification step just can use.Another advantage of the inventive method is that the production of oxidation-stabilized biofuel can be carried out at low temperatures with in the relative short time.Therefore, method of the present invention might be improved the economy of the production of oxidation-stabilized biofuel.Compare with 20% liquid main anti-oxidant, because described liquid contains the active ingredient antioxidant of only about 20% weight usually, so the active quantities of the liquid main anti-oxidant of Shi Yonging is 100% in the present invention according to prior art.Use can be saved transportation and storage cost equally according to the liquid main anti-oxidant of the inventive method, because the cause of the high reactivity content of main anti-oxidant in every liter.Use also causes in the biofuel or the crystallization of main anti-oxidant minimizing at low temperatures in factory component according to the liquid main anti-oxidant of the inventive method.
The invention provides a kind of method that increases the oxidative stability of biofuel, it comprises that fusing point is less than or equal to 40 ℃ main anti-oxidant to join with the amount of 10-20000ppm (w/w) and treat in the stable biofuel that wherein said main anti-oxidant comprises at least a compound with formula I structure
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
Wherein
*Be the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, has the straight chained alkyl of 1-40 carbon atom, wherein type R
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
The present invention also provides fusing point to be less than or equal to 40 ℃ and comprise the purposes that at least a main anti-oxidant with compound of formula I structure is used to increase the oxidative stability of biofuel,
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
Wherein
*Be the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, has the straight chained alkyl of 1-40 carbon atom, wherein type R
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
The present invention equally also provides a kind of oxidation-stabilized biofuel, and its fusing point that comprises 10-20000ppm (w/w) is less than or equal to 40 ℃ and comprise at least a main anti-oxidant with formula I structural compounds,
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
Wherein
*Be the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, has the straight chained alkyl of 1-40 carbon atom, wherein type R
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
The method of the present invention that increases the oxidative stability of biofuel comprises fusing point or is less than or equal to 40 ℃ main anti-oxidant and joins with the amount of 10-20 000ppm (w/w) and treat in the stable biofuel that wherein said main anti-oxidant comprises at least a compound with formula I structure
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
Wherein
*Be the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, has the straight chained alkyl of 1-40 carbon atom, wherein type R
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
Concerning the object of the invention, main anti-oxidant is the mixture of compound or compound, undesirable DeR that its inhibition or prevent causes by oxygen in the biofuel.The mode of action of these main anti-oxidants in biofuel is described in the following reaction scheme, wherein R and R ' each be organic group, and AOH is the main anti-oxidant that uses in the method for the invention.
1. chain initiation
2. chainpropagation
3. chain termination
Except that above-mentioned reaction, on two keys of fatty acid alkyl ester, also may react, it may be caused by oxygen equally.Here, be positioned at respect to the C-H of the allylic positions of described pair of key and preferentially attacked by oxygen:
The main anti-oxidant of Shi Yonging neither comprises organic solvent such as alcohol does not contain biofuel situation as described yet in the method for the invention, for example, and when using masterbatch.Therefore, employed main anti-oxidant preferably only comprises the alkylphenol of alkylphenol and/or replacement.Especially, the mixture that contains various replacements and/or unsubstituted alkyl phenol, preferably contain 0.1-99.9% weight, more preferably the mixture of the compound of one or more structure I of 50-99% weight and preferred especially 55-90% weight is used as main anti-oxidant in the method for the invention.
In the method for the invention, preferred especially use only contains the mixture of structure I compound as main anti-oxidant.The advantage of this mixture is that it only contains the structure I compound, and this structure I compound all has oxidation-stabilized effect to biofuel.
In the method for the invention, the preferred use contains at least a main anti-oxidant with structure I I compound
Wherein:
R
1, R
2=hydrogen, have 1-4 carbon atom straight chained alkyl or
Wherein
*Be the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-4 carbon atom,
R
4=hydrogen, has the straight chained alkyl of 1-4 carbon atom, wherein type R
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
In the method for the invention, preferably in biofuel, add and contain at least a main anti-oxidant with structure III compound
In the method for the invention, preferably in biofuel, add and contain at least a main anti-oxidant with structure I V compound,
In addition, the main anti-oxidant that uses in the method for the invention can only comprise and is selected from following compound:
-three-tert-butyl phenol, particularly 2,4,6-three-tert.-butyl phenol,
-two-tert-butyl phenol, particularly 2,4-two-tert.-butyl phenol, 2,5-two-tert.-butyl phenol, 2,6-two-tert.-butyl phenol,
-two-tertiary butyl methylbenzene phenols, particularly 2,5-two-tertiary butyl-4-methylphenol, 2,6-two-tertiary butyl-4-methylphenol, 4,6-two-tertiary butyl-2-methylphenol, two-tertiary butyl-3-methylphenol,
-tertiary butyl methylbenzene phenols, particularly the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 4-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol,
-tertiary butyl dimethyl benzene phenols, particularly the 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol, the tertiary butyl-2, the 5-xylenol,
-tert-butyl phenol, particularly 2-tert.-butyl phenol, 4-tert.-butyl phenol,
-two-sec-butylbenzene phenols,
-sec-butylbenzene phenols, particularly 2-sec-butyl phenol, 2-sec-butyl-4-tert.-butyl phenol, 4-sec-butyl-2,6-two-tert.-butyl phenol,
-tert.-amylbenzene phenols, particularly 2-tert.-amyl phenol,
-two-tert.-amylbenzene phenols, particularly 2,4-two-tert.-amyl phenol,
-2-isopropyl-phenol, 4-octyl phenol, 4-nonylphenol, 2,6-two-tertiary butyl-4-nonylphenol, 4-dodecyl phenol and/or octadecyl phenol, and the mixture of these compounds, wherein this main anti-oxidant has and is less than or equal to 40 ℃ fusing point.
Fusing point is not included in the scope of the present invention greater than the pure substance of structure I-IV compound of 40 ℃ or the mixture that contains them.
In the method for the invention the main anti-oxidant of Shi Yonging have≤40 ℃, preferred≤39 ℃, and preferred especially≤38 ℃ fusing point.
The inferior antioxidant that can use in the method for the invention is an alkylthio methylbenzene phenols, is preferably selected from:
-2,4-two ((hot sulfenyl) methyl)-6-tert.-butyl phenol,
-2,4-two ((hot sulfenyl) methyl)-6-methylphenol,
-2,4-two ((hot sulfenyl) methyl)-6-ethylphenol and
-2,6-two ((dodecane sulfenyl) methyl)-4-nonylphenol,
Hydroxylated diphenylsulfide class is preferably selected from:
-2,2 '-sulfo-two [the 6-tertiary butyl-4-methylphenol],
-2,2 '-sulfo-two [4-octyl phenol],
-4,4 '-sulfo-two [the 6-tertiary butyl-3-methylphenol],
-4,4 '-sulfo-two [the 6-tertiary butyl-2-methylphenol],
-4,4 '-sulfo-two [3,6-two-sec.-amyl sec-pentyl secondary amyl phenol] and
-4,4 '-two [2,6-dimethyl-4-hydroxy phenyl] disulphide,
Phosphorous acid esters or phosphinate are preferably selected from
-triphenyl phosphite,
-diphenyl alkyl phosphorous acid ester,
-phenyl dialkyl phosphorous acid ester,
-three [nonyl phenyl] phosphorous acid ester,
-three lauryl phosphorous acid esters,
-three-octadecyl phosphorous acid ester,
-distearyl tetramethylolmethane base (pentaerythrityl) diphosphites,
-three [2,4-two-tert-butyl-phenyl] phosphorous acid ester,
-diiso decyl tetramethylolmethane base diphosphites,
-two [2,4-two-tert-butyl-phenyl] tetramethylolmethane base diphosphites,
-two [2,6-two-tertiary butyl-4-aminomethyl phenyl] tetramethylolmethane base diphosphites,
-two [isodecyl oxygen base] tetramethylolmethane base diphosphites,
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] tetramethylolmethane base diphosphites,
-two [2,4,6-three-tert-butyl-phenyl] tetramethylolmethane base diphosphites,
-three stearyl Sorbitol Powder GW-540s,
-four [2,4-two-tert-butyl-phenyl]-4,4 '-biphenylene (biphenylene), two phosphinates,
-6-different octyloxy-2,4,8,10-four-tertiary butyl-12H-dibenzo [d, g]-1,3,2-dioxaphosphocine,
-6-fluoro-2,4,8,10-four-tertiary butyl-12-methyldiphenyl is [d, g]-1,3 also, 2-dioxaphosphocine,
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] methyl phosphorous acid esters and
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] ethide phosphite ester,
Or the compound of destruction superoxide, be preferably selected from
The ester of-β-thio-2 acid, the ester of preferred lauryl, stearyl, myristyl or tridecyl,
-mercaptobenzimidazole,
The zinc salt of-2-mercaptobenzimidazole,
-zinc dibutyl dithiocarbamate,
-two-octadecyl disulphide and
-tetramethylolmethane base four [β-dodecyl sulfydryl] propionic ester,
Or the mixture of these compounds.
For the purposes of the present disclosure, the term biofuel comprises the methyl ester or the ethyl ester of all saturated and/or undersaturated alkyl esters, particularly lipid acid of lipid acid, and it can be used as energy carrier and uses.For the purposes of the present disclosure, energy carrier comprises the fuel as thermal source, as heating material and provide vehicle such as the fuel of automobile, lorry, steamer or aircraft power.The biofuel that the employed biofuel of the inventive method is preferably sold with title biodiesel on market usually as automobile fuel.Especially, the employed biofuel of the inventive method comprises C
12-C
24Fatty acid alkyl ester, preferred C
12-C
24Fatty acid methyl ester or C
12-C
24Fatty-acid ethyl ester, it can exist with pure form or with the form of mixture.In addition, the employed biofuel of the inventive method can also comprise all conventional additives as follows antioxidant, defoamer, the mobile activator of low temperature.Method of the present invention is preferably used by plant and/or animal oil by carrying out the biofuel that transesterification makes with pure particular methanol or the special particular methanol of ethanol.Method of the present invention is more preferably used the biofuel of the transesterification products that contains rapeseed oil, soybean oil, sunflower oil, plam oil (palm kerneloil), Oleum Cocois, curcas oil, Oleum Gossypii semen, peanut oil, Semen Maydis oil and/or used cooking oil.Yet, especially preferably use the biofuel that from rapeseed oil, sunflower oil or soybean oil, obtains by above-mentioned transesterification.Method of the present invention also is applied in the mixture of transesterification products of each kind of plant and/or animal oil.
In a kind of particular of the inventive method, the mixture of saturated and/or unsaturated fatty acids acid alkyl ester and liquid energy carrier, for example mineral diesel fuel or oil fuel can be used as biofuel.Especially preferably use the mixture of the saturated and/or unsaturated fatty acids acid alkyl ester of mineral diesel fuel and 0.1-99.9% volume, particularly 2-10% volume and preferred 3-5% volume.In the later step of the inventive method, can be in the liquid energy carrier particularly in mineral diesel fuel or oil fuel, add consumption and be 0.1-99.9% volume, particularly 1-20% volume, preferred 2-10% volume and the more preferably oxidation-stabilized biofuel of 3-5% volume.
In the method for the invention, the preferred main anti-oxidant that directly adds particularly directly adds consumption and is 10-20000ppm (w/w), preferably 50-12000ppm (w/w) and the more preferably main anti-oxidant of 100-8000ppm (w/w).For the purposes of the present disclosure, directly adding is meant solution or the masterbatch that is not prepared main anti-oxidant in step before.In this step, can also be with the consumption 10-20000ppm (w/w), preferred 50-12000ppm (w/w) and more preferably 100-8000ppm (w/w) in this biofuel, adds inferior antioxidant.
Preferably 18 ℃-60 ℃, more preferably in 20 ℃-40 ℃ temperature range, stir down described main anti-oxidant be dissolved in the described biofuel.
The purposes that the present invention also provides main anti-oxidant to be used to increase the oxidative stability of biofuel, described main anti-oxidant have and are less than or equal to 40 ℃ fusing point and comprise at least a compound with formula I structure.
Preferred especially use only comprises compound with the formula I structure mixture as main anti-oxidant.The advantage of this mixture is that it only comprises the compound with formula I structure, and the compound of its Chinese style I structure all has oxidation-stabilized effect to biofuel.The preferred use comprises at least a main anti-oxidant with compound of formula II structure.Yet, more preferably use to comprise at least a main anti-oxidant with compound of formula III structure.Preferred especially the use comprises at least a main anti-oxidant with compound of formula IV structure.
In addition, also may use and only comprise the main anti-oxidant that is selected from following compound:
-three-tert-butyl phenol, particularly 2,4,6-three-tert.-butyl phenol,
-two-tert-butyl phenol, particularly 2,4-two-tert.-butyl phenol, 2,5-two-tert.-butyl phenol, 2,6-two-tert.-butyl phenol,
-two-tertiary butyl methylbenzene phenols, particularly 2,5-two-tertiary butyl-4-methylphenol, 2,6-two-tertiary butyl-4-methylphenol, 4,6-two-tertiary butyl-2-methylphenol, two-tertiary butyl-3-methylphenol,
-tertiary butyl methylbenzene phenols, particularly the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 4-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol,
-tertiary butyl dimethyl benzene phenols, particularly the 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol, the tertiary butyl-2, the 5-xylenol,
-tert-butyl phenol, particularly 2-tert.-butyl phenol, 4-tert.-butyl phenol,
-two-sec-butylbenzene phenols,
-sec-butylbenzene phenols, particularly 2-sec-butyl phenol, 2-sec-butyl-4-tert.-butyl phenol, 4-sec-butyl-2,6-two-tert.-butyl phenol,
-tert.-amylbenzene phenols, particularly 2-tert.-amyl phenol,
-two-tert.-amylbenzene phenols, particularly 2,4-two-tert.-amyl phenol,
-2-isopropyl-phenol, 4-octyl phenol, 4-nonylphenol, 2,6-two-tertiary butyl-4-nonylphenol, 4-dodecyl phenol and/or octadecyl phenol, and the mixture of these compounds, wherein this main anti-oxidant has and is less than or equal to 40 ℃ fusing point.
Fusing point is not included in the scope of the present invention greater than the pure substance of structure I-IV compound of 40 ℃ or the mixture that comprises them.
Oxidation-stabilized biofuel of the present invention comprises 10-20000ppm (w/w), preferred 50-12000ppm (w/w) and more preferably 100-8000ppm (w/w) quantity, fusing point are less than or equal to 40 ℃ and comprise at least a main anti-oxidant with compound of formula I structure.
Therefore, the main anti-oxidant of oxidation-stabilized biofuel of the present invention preferably only comprises the induced by alkyl hydroxybenzene of induced by alkyl hydroxybenzene and/or replacement.Especially, oxidation-stabilized biofuel of the present invention comprises mixture various replacements and/or the unsubstituted alkyl phenols as main anti-oxidant.Biofuel of the present invention preferably comprises and contains 0.1-99.9% weight, more preferably one or more of 50-99% weight and preferred especially 55-99% weight have the main anti-oxidant of the compound of structure I.Biofuel of the present invention especially preferably comprises a kind of mixture, this mixture only comprise have structure I compound as main anti-oxidant.
Biofuel of the present invention preferably comprises and contains at least a main anti-oxidant with compound of structure I I.Biofuel of the present invention more preferably comprises and contains at least a main anti-oxidant with compound of structure III.Biofuel of the present invention especially preferably comprises and contains at least a main anti-oxidant with compound of structure I V.
In addition, biofuel of the present invention can comprise and only contain the main anti-oxidant that is selected from following compound:
-three-tert-butyl phenol, particularly 2,4,6-three-tert.-butyl phenol,
-two-tert-butyl phenol, particularly 2,4-two-tert.-butyl phenol, 2,5-two-tert.-butyl phenol, 2,6-two-tert.-butyl phenol,
-two-tertiary butyl methylbenzene phenols, particularly 2,5-two-tertiary butyl-4-methylphenol, 2,6-two-tertiary butyl-4-methylphenol, 4,6-two-tertiary butyl-2-methylphenol, two-tertiary butyl-3-methylphenol,
-tertiary butyl methylbenzene phenols, particularly the 2-tertiary butyl-4-methylphenol, the 6-tertiary butyl-2-methylphenol, the 4-tertiary butyl-2-methylphenol, the 6-tertiary butyl-3-methylphenol,
-tertiary butyl dimethyl benzene phenols, particularly the 4-tertiary butyl-2,6-xylenol, the 6-tertiary butyl-2,4-xylenol, the tertiary butyl-2, the 5-xylenol,
-tert-butyl phenol, particularly 2-tert.-butyl phenol, 4-tert.-butyl phenol,
-two-sec-butylbenzene phenols,
-sec-butylbenzene phenols, particularly 2-sec-butyl phenol, 2-sec-butyl-4-tert.-butyl phenol, 4-sec-butyl-2,6-two-tert.-butyl phenol,
-tert.-amylbenzene phenols, particularly 2-tert.-amyl phenol,
-two-tert.-amylbenzene phenols, particularly 2,4-two-tert.-amyl phenol,
-2-isopropyl-phenol, 4-octyl phenol, 4-nonylphenol, 2,6-two-tertiary butyl-4-nonylphenol, 4-dodecyl phenol and/or octadecyl phenol, and the mixture of these compounds.
Especially, biofuel of the present invention comprises C
12-C
24Fatty acid alkyl ester, preferred C
12-C
24Fatty acid methyl ester or C
12-C
24Fatty-acid ethyl ester, it can exist with pure form or with the form of mixture.In addition, biofuel of the present invention can also comprise all conventional additives as follows antioxidant, defoamer.Biofuel of the present invention preferably comprises the transesterification products of rapeseed oil, soybean oil, sunflower oil, plam oil, Oleum Cocois, curcas oil and/or used cooking oil.Biofuel of the present invention especially preferably comprises the transesterification products that obtains by transesterification from rapeseed oil, sunflower oil or soybean oil.Biofuel of the present invention can also comprise the mixture of the transesterification products of each kind of plant and/or animal oil.
In addition, biofuel of the present invention can further comprise all conventional additives as follows antioxidant, defoamer, cold flow improver.The inferior antioxidant that can exist in biofuel of the present invention is an alkylthio methylbenzene phenols, is preferably selected from
-2,4-two ((hot sulfenyl) methyl)-6-tert.-butyl phenol,
-2,4-two ((hot sulfenyl) methyl)-6-methylphenol,
-2,4-two ((hot sulfenyl) methyl)-6-ethylphenol and
-2,6-two ((dodecane sulfenyl) methyl)-4-nonylphenol,
Hydroxylated diphenylsulfide class is preferably selected from
-2,2 '-sulfo-two [the 6-tertiary butyl-4-methylphenol],
-2,2 '-sulfo-two [4-octyl phenol],
-4,4 '-sulfo-two [the 6-tertiary butyl-3-methylphenol],
-4,4 '-sulfo-two [the 6-tertiary butyl-2-methylphenol],
-4,4 '-sulfo-two [3,6-two-sec.-amyl sec-pentyl secondary amyl phenol] and
-4,4 '-two [2,6-dimethyl-4-hydroxy phenyl] disulphide,
Phosphorous acid esters or phosphinate are preferably selected from
-triphenyl phosphite,
-diphenyl alkyl phosphorous acid ester,
-phenyl dialkyl phosphorous acid ester,
-three [nonyl phenyl] phosphorous acid ester,
-three lauryl phosphorous acid esters,
-three-octadecyl phosphorous acid ester,
-distearyl tetramethylolmethane base diphosphites,
-three [2,4-two-tert-butyl-phenyl] phosphorous acid ester,
-diiso decyl tetramethylolmethane base diphosphites,
-two [2,4-two-tert-butyl-phenyl] tetramethylolmethane base diphosphites,
-two [2,6-two-tertiary butyl-4-aminomethyl phenyl] tetramethylolmethane base diphosphites,
-two [isodecyl oxygen base] tetramethylolmethane base diphosphites,
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] tetramethylolmethane base diphosphites,
-two [2,4,6-three-tert-butyl-phenyl] tetramethylolmethane base diphosphites,
-three stearyl Sorbitol Powder GW-540s,
-four [2,4-two-tert-butyl-phenyl]-4,4 '-biphenylene, two phosphinates,
-6-different octyloxy-2,4,8,10-four-tertiary butyl-12H-dibenzo [d, g]-1,3,2-dioxaphosphocine,
-6-fluoro-2,4,8,10-four-tertiary butyl-12-methyldiphenyl is [d, g]-1,3 also, 2-dioxaphosphocine,
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] methyl phosphorous acid esters and
-two [2,4-two-tertiary butyl-6-aminomethyl phenyl] ethide phosphite ester,
Or the compound of destruction superoxide, be preferably selected from:
The ester of-β-thio-2 acid, the ester of preferred lauryl, stearyl, myristyl or tridecyl,
-mercaptobenzimidazole,
The zinc salt of-2-mercaptobenzimidazole,
-zinc dibutyl dithiocarbamate,
-two-octadecyl disulphide and
-tetramethylolmethane base four [β-dodecyl sulfydryl] propionic ester,
Or the mixture of these compounds.
In biofuel of the present invention, these times antioxidant can be with 10-20 000ppm (w/w), preferred 50-12 000ppm (w/w) and the more preferably quantity existence of 100-8000ppm (w/w).
Biofuel of the present invention preferably uses method of the present invention to be prepared.
The following examples are used for illustrating method of the present invention, rather than the present invention is limited to this embodiment.
Specific embodiments
The preparation of embodiment 1-sample
In glass beaker, stir down main anti-oxidant is dissolved in the biofuel in 20 ℃, continue to stir till obtaining the clear solution of main anti-oxidant in biofuel.Employed main anti-oxidant, employed biofuel and schedule of proportion are shown in the table 1.
The composition of the employed main anti-oxidant of embodiment 2-
Main anti-oxidant 1
(obtaining with trade name IONOL 99) from Degussa AG:
2 of＞99.0% weight, 6-two-tert.-butyl phenol
The 2-tert.-butyl phenol of＜0.5% weight
2 of＜0.5% weight, 4-two-tert.-butyl phenol
Main anti-oxidant 2
(obtaining with trade name IONOL K98) from Degussa AG:
The 6-tertiary butyl-2 of＞98.5% weight, the 4-xylenol
The 4-tertiary butyl-2 of＜1.5% weight, 6-xylenol and two-tertiary butyl methyl-phenol
Main anti-oxidant 3
(obtaining with trade name IONOL K65) from Degussa AG:
The 6-tertiary butyl-2 of＞55% weight, the 4-xylenol
2 of＞15% weight, 6-two-tertiary butyl-4-methylphenol
The tertiary butyl of 18-22% weight-2, the 5-xylenol
4 of＜1% weight, 6-two-tertiary butyl-2-methylphenol
Two-tertiary butyl of＜3.5% weight-3-methylphenol
2 of＜3.5% weight, 5-two-tertiary butyl-4-methylphenol
Main anti-oxidant 4
(obtaining with trade name IONOL 75) from Degussa AG:
2 of＞75% weight, 6-two-tert.-butyl phenol
The 2-tert.-butyl phenol of＜5% weight
The 4-tert.-butyl phenol of＜0.5% weight
2 of＜3% weight, 4-two-tert.-butyl phenol
2 of＜1% weight, 5-two-tert.-butyl phenol
2,4 of＜15.5% weight, 6-three-tert.-butyl phenol
Embodiment 3-testing method
The oxidative stability of Zhi Bei sample is tested according to testing method DIN EN 14112 under 110 ℃ probe temperature as described in example 1 above.
The result of embodiment 4-testing method
| Antioxidant | The quantity of liquid antioxidant [ppm] | Oxidative stability [time under 110 ℃ (h)] |
| Rapeseed methylester | ||
| - | - | 5.1 |
| 1 | 500 | 6.7 |
| 2 | 500 | 6.5 |
| 3 | 500 | 6.6 |
| 4 | 500 | 6.7 |
| Baynox * | 2500 | 7.1 |
| The fatty methyl esters of used culinary art | ||
| - | - | 4.0 |
| 1 | 2000 | 9.7 |
| 2 | 2000 | 9.5 |
| 3 | 2000 | 9.1 |
| 4 | 2000 | 9.4 |
| Baynox * | 10000 | 12.0 |
| The soybean oil methyl esters | ||
| - | - | 3.6 |
| 1 | 2000 | 7.3 |
| 2 | 2000 | 6.6 |
| 3 | 2000 | 6.3 |
| 4 | 2000 | 7.1 |
| Baynox * | 10000 | 8.8 |
| The sunflower oil methyl esters | ||
| - | - | 1.6 |
| 1 | 4000 | 8.8 |
| 2 | 4000 | 7.8 |
| 3 | 4000 | 6.9 |
| 4 | 4000 | 8.0 |
| Baynox * | 20000 | 9.0 |
*Baynox be a kind of from Lanxess antioxidant and be a kind of distilled, the high-purity solution of active ingredient in biofuel.Active quantities has been set as 20%g/l, like this 1L Baynox
The active ingredient that is equivalent to 200g.Analytical results shows: Baynox
In active ingredient be 2,6-two-tertiary butyl-4-hydroxy toluene.
Claims (7)
1. method that increases the oxidative stability of biofuel, it comprises and fusing point is less than or equal to 40 ℃ main anti-oxidant joins with the amount of 10-20000ppm (w/w) and treat in the stable biofuel, wherein said main anti-oxidant comprises at least a compound with structure I
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
, wherein * is the carbon atom of aromatics ring system,
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, have the straight chained alkyl of 1-40 carbon atom,
Type R wherein
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
2. the process of claim 1 wherein that one or more mixtures with compound of structure I that comprise 0.1-99.9% weight are used as main anti-oxidant.
3. the process of claim 1 wherein that the mixture that only comprises the compound with structure I is used as main anti-oxidant.
4. at least one described method of claim 1-3, wherein said main anti-oxidant comprises at least a compound with structure III
5. at least one described method of claim 1-3, wherein said main anti-oxidant comprises at least a compound with structure I V
6. fusing point is less than or equal to 40 ℃ and comprise the purposes that at least a main anti-oxidant with compound of structure I is used to increase the oxidative stability of biofuel
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, have the straight chained alkyl of 1-40 carbon atom,
Type R wherein
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
7. oxidation-stabilized biofuel, it comprises fusing point and is less than or equal to 40 ℃ and comprise at least a main anti-oxidant with 10-20000ppm (w/w) of the compound of structure I,
Wherein:
R
1, R
2=hydrogen, have 1-20 carbon atom straight chained alkyl or
R
3, R
5=hydrogen, have the straight chained alkyl of 1-20 carbon atom,
R
4=hydrogen, have the straight chained alkyl of 1-40 carbon atom,
Type R wherein
1And R
2Substituting group and type R
3And R
5Substituting group be identical or different in each case.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005015474.3 | 2005-04-04 | ||
| 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 |
|---|---|
| CN1847369A true CN1847369A (en) | 2006-10-18 |
Family
ID=36645651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100719299A Pending CN1847369A (en) | 2005-04-04 | 2006-04-03 | 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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| 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 |
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| 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 |
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-
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 KR KR1020060030620A patent/KR20060106903A/en not_active Application Discontinuation
- 2006-04-04 BR BRPI0601216-7A patent/BRPI0601216A/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20060106903A (en) | 2006-10-12 |
| AR054335A1 (en) | 2007-06-20 |
| CA2541591A1 (en) | 2006-10-04 |
| EP1736528A2 (en) | 2006-12-27 |
| AU2006201342A1 (en) | 2006-10-19 |
| NZ546249A (en) | 2007-08-31 |
| JP2006283028A (en) | 2006-10-19 |
| BRPI0601216A (en) | 2006-12-05 |
| SG126070A1 (en) | 2006-10-30 |
| EP1736528A3 (en) | 2007-01-10 |
| DE102005015474A1 (en) | 2006-10-05 |
| US20060218855A1 (en) | 2006-10-05 |
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