CN1087668A - 含铜芳香曼尼齐络合物及浓缩物和含此物质的柴油机燃料 - Google Patents
含铜芳香曼尼齐络合物及浓缩物和含此物质的柴油机燃料 Download PDFInfo
- Publication number
- CN1087668A CN1087668A CN93114211A CN93114211A CN1087668A CN 1087668 A CN1087668 A CN 1087668A CN 93114211 A CN93114211 A CN 93114211A CN 93114211 A CN93114211 A CN 93114211A CN 1087668 A CN1087668 A CN 1087668A
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- China
- Prior art keywords
- copper
- fuel
- diesel
- component
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 89
- 239000000446 fuel Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 229940116318 copper carbonate Drugs 0.000 claims description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 238000011017 operating method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000010992 reflux Methods 0.000 description 17
- 150000004699 copper complex Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- -1 alkenyl amine Chemical class 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229930040373 Paraformaldehyde Natural products 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 229920002866 paraformaldehyde Polymers 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical group CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 241000208202 Linaceae Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-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
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- RDCVZFGRXFJZDF-UHFFFAOYSA-N phenol;prop-1-ene Chemical compound CC=C.CC=C.CC=C.CC=C.OC1=CC=CC=C1 RDCVZFGRXFJZDF-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- BLSQLHNBWJLIBQ-OZXSUGGESA-N (2R,4S)-terconazole Chemical compound C1CN(C(C)C)CCN1C(C=C1)=CC=C1OC[C@@H]1O[C@@](CN2N=CN=C2)(C=2C(=CC(Cl)=CC=2)Cl)OC1 BLSQLHNBWJLIBQ-OZXSUGGESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000005752 Copper oxychloride Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 1
- BWLYQXJZLBBGCK-UHFFFAOYSA-N copper;dodecanoic acid Chemical compound [Cu].CCCCCCCCCCCC(O)=O BWLYQXJZLBBGCK-UHFFFAOYSA-N 0.000 description 1
- GYPBUYJSHBFNEJ-UHFFFAOYSA-L copper;hexadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GYPBUYJSHBFNEJ-UHFFFAOYSA-L 0.000 description 1
- QVLQKWQNKGVECJ-UHFFFAOYSA-N copper;propanoic acid Chemical compound [Cu].CCC(O)=O QVLQKWQNKGVECJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229940089256 fungistat Drugs 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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Abstract
本发明涉及含铜芳香络合物、浓缩物及含同样络
合物的柴油机燃料。这种柴油机燃料有益于装有排
气系统颗粒收集器的柴油发动机。含铜芳香曼尼齐
络合物可用于降低收集于收集器中废气颗粒的引燃
温度,它是由组分(A)或组分(B)与组分(C)一种铜反
应物反应而制得的。组分(A)和(B)(I)、B(II)通式如
上,式中各基团含意见说明书。
Description
本发明涉及含铜芳香曼尼齐络合物、浓缩物及含该络合物的柴油机燃料,该柴油机燃料有益于装有排气系统颗粒收集器的柴油发动机。使用含铜芳香曼尼齐络合物可降低收集于收集器中废气颗粒的引燃温度。
柴油发动机已被用作路面上行驶车辆的发动机,这是因为它有较低成本并提高效率。可是,由于柴油发动机的运行特点,与汽油发动机相比,它排放出大量的碳黑粒子或很细的凝结粒子或其凝聚物。这些颗粒或凝结物有时也称作“柴油烟灰”。排放这种颗粒或烟灰导致了环境污染。这是人们所不需要的。更有甚者,已观察到柴油烟灰中富含凝结的多环烃,其中一些烃被认为是致癌的。因此人们为柴油发动机的使用设计了收集碳黑和凝结颗粒的颗粒收集器或过滤器。
颗粒收集器或过滤器通常是由阻热过滤器与电加热器组成,阻热过滤器是由多孔状的陶瓷或金属纤维组成的,电加热器用来加热并引燃过滤器中收集的碳黑颗粒。由于通常运行条件下,柴油发动机废气温度不足以烧去过滤器或收集器中积累的柴油烟灰,所以加热器是必需的。一般来说,这需要约450-600℃的温度,加热器弥补了废气温度的不足,以便引燃收集器中的颗粒使收集器再生。另外,碳黑的积累最终使收集器堵塞,引起废气反压增加,导致运行问题。上述热收集器没有完全解决该问题,这是因为当车辆在正常条件下运行时,排出废气温度比碳黑颗粒引燃温度低以及大量流动的废气带走电热器产生的热所致。解决此问题的一方法是周期性地富集柴油发动机中燃烧的空气/燃料混合物以产生较高的废气温度从而使收集器达到较高的温度。然而,较高的温度引起收集器的再生失控而导致局部温度升高使收集器损坏。
也曾有建议:降低颗粒的引燃温度以使颗粒在最低可能温度下开始燃烧可以控制收集器中颗粒的形成。降低引燃温度的一种方法是于废气颗粒中加入燃烧改进剂。向废气颗粒中加入燃烧改进剂的最实用途径是向燃料中加入。已提出铜化合物可作为包括柴油机燃料在内的燃料燃烧改进剂。
美国环境保护署(EPA)估测公路上柴油机燃料的平均硫含量约为0.25%(重量百分数),要求到1993年10月1日降至不超过0.05%(重量百分数)。环境保护署还要求柴油机燃料最低十六烷指数规格为40(或最大芳香水平为35%)。该规则目标为降低硫酸盐颗粒和含碳有机颗粒的排放。参见:联邦登记簿,第55卷,第162号,1990年8月21日,第34120-34151页。商业上满足这些排放要求的低硫柴油机燃料和技术还未实施。满足这些排放要求的一种方法是提供低硫柴油机燃料添加剂。该添加剂用于低硫柴油机燃料环境中可有效地降低柴油发动机颗粒收集器收集的油灰引燃温度。
美国专利3,346,493公开了润滑剂的配方,它们含有金属络合物,它们是由烃取代琥珀酸化合物(如聚异丁烯基取代的琥珀酸酐)与链烯基胺(如聚亚烷基多胺)的反应产物所制成,通过与至少约0.1当量的形成络合物的金属化合物与该反应产物反应而制成该络合物。金属的原子数为24-30(即Cr、Mn、Fe、Co、Ni、Cu和Zn)。
美国专利4,673,412公开了燃料组合物(如柴油机燃料、馏分燃料、燃料油、残余燃料、船用锅炉燃料),它们含金属化合物和肟。文献表明这种含此结合形式的燃料储存稳定,可有效地减少内燃机废气中的油灰的形成。优选金属化合物是曼尼齐碱的过渡金属络合物,该曼尼齐碱可由(A)芳香酚、(B)醛或酮和(C)羟基和/或含硫醇胺衍生而来。理想的金属为Cu、Fe、Zn、Co、Ni和Mn。
美国专利4,816,038公开了含羟基和/或含硫醇芳香曼尼齐的过渡金属络合物与西佛碱的反应产物的燃料组合物(如柴油机燃料、馏分燃料、燃料油、残余燃料、船用锅炉燃料)。文献表明这种含此结合形式的燃料储存稳定,可有效地减少内燃机废气中油灰的形成,曼尼齐可由(A)含羟基和/或含硫醇芳香物、(B)醛或酮和(C)含羟基和/或含硫醇胺衍生。理想的金属为Cu、Fe、Zn和Mn。
国际出版物No.WO88/02392公开了装有排气系统颗粒收集器(以降低收集于收集器中废气颗粒累积)的柴油机的操作方法,该方法包括使用含有效数量的钛或锆化合物或络合物的燃料(以降低收集于收集器中废气颗粒的引燃温度)开动柴油发动机。
该发明涉及含铜芳香曼尼期络合物、浓缩物及含同样络合物的柴油机燃料,这种柴油机燃料有益于装有排气系统颗粒收集器的柴油发动机。含铜芳香曼尼齐络合物可用于隆低收集于收集器中废气颗粒的引燃温度,该含铜芳族曼尼期络合物由组份(A)或组份(B)与组份(C)相接触而制得。
组份(A)至少是由如下结构式
表示的一种化合物,R1为含1-约6个碳原子的烷基,R2为约16-20个碳原子的饱和的或不饱和的脂肪族烃基。
组份(B)是(B)(Ⅰ)和(B)(Ⅱ)的混合物,组份(B)(Ⅰ)至少是由如下结构式
表示的一种化合物,式中R3为约9-18个碳原子的烷基,R4为1-约4个碳原子的亚烷基,R5为约16-20个碳原子的饱和的或不饱和的脂肪族烃基,组分(B)(Ⅱ)至少是由如下结构式
表示的一种化合物,式中R6和R8为约9-18个碳原子的烷基,这两个烷基互不相关,R7为1-约4个碳原子的亚烷基。
组份(C)至少为一铜反应物
本发明的芳香曼尼齐络合物在柴油机燃料中是可溶的或稳定分散的,在柴油燃料中,25℃时,该络合物的溶解度至少1克/升。25℃时,在柴油机燃料中稳定可分散的或稳定分散的络合物能保持至少约24小时的分散状态。
组份(A)至少是如下结构式
表示的一种化合物,R1为1-约6个碳原子的烷基,约3-5个碳原子更好,约4个碳原子最好。R2为约16-20个碳原子的饱和的或不饱和的脂肪烃基,约18个碳原子更好。在一具体实例中,R1为叔丁基,R2可为油基、棕榈基、硬脂基、廿烷基、棕榈油基、亚油基或亚麻基,优选油基。R2可以是两个或更多的上述烃基的混合体,动物脂便是一例。
组份(B)(Ⅰ)至少是如下结构式
表示的一种化合物,式中R3是约9~18个碳原子的烷基,约10~14个碳原子更好,约12个碳原子最好。R4是1-约4个碳原子的亚烷基,2或3个碳原子更好。R5是约16-20个碳原子的饱和的或不饱和的脂肪烃基,约18个碳原子更好。在一具体实例中,R3为十二烷基或四聚丙烯基。在一具体实例中,R4为亚丙基或三亚甲基,R5可为油基、棕榈基、硬脂基、廿烷基、棕榈油基、亚油基或亚麻基,优选油基。R5可以是两个或更多的上述烃基的混合体。动物脂便是一例。
组份(B)(Ⅱ)至少是如下结构式
表示的一种化合物。式中R6和R8为约9-18个碳原子的烷基,这两个烷基互不相关,约10-14个碳原子更好,约12个碳原子最好。R7为1-约4个碳原子的亚烷基,2个或3个碳原子更好。在一具体实施例中,R6和R8为十二烷基或四聚丙烯基。在一具体实例中,R7为亚乙基。
芳香曼尼齐(A)、(B)(Ⅰ)和(B)(Ⅱ)为烷基取代的酚、甲醛或其前体(如多聚甲醛)和胺衍生而来。
酚为具有下列结构式的化合物
这里R同上面限定的R1、R3、R6或R8。最好甲醛是多聚甲醛。
当芳香曼尼齐是组份(A)时,胺为如下结构式所代表的化合物
H2NR2
这里R2定义同上。在一具体实例中,该胺为油胺。酚、甲醛、胺的摩尔比最好约为1∶1∶1。
当芳香曼尼齐是组份(B)(Ⅰ)时,胺为如下结构式所代表的化合物
H2NR4NHR5
这里R4和R5定义同上。在一具体实例中,该胺为N-油基-1,3-二胺基丙烷。酚、甲醛、胺的摩尔比最好约为1∶1∶1。
当芳香曼尼齐为组份(B)(Ⅱ)时,该胺为如下结构式所代表的化合物
H2NR7OH
这里R7定义同上。在一具体实例中,该胺为一乙醇胺、酚、甲醛、胺的摩尔比最好约为2∶2∶1。
芳香曼尼齐(A)、(B)(Ⅰ)和(B)(Ⅱ)的制备可以按文献中已知的许多方法进行。一种方法是将酚、甲醛或其前体和胺加入到合适的容器中加热进行反应。反应温度可从室温到不超过任何组份或芳香曼尼齐产物的分解温度。反应期间,可用鼓泡法除去水份,使用诸如芳香型油等溶剂进行该反应是令人满意的。
在另一种制备芳香曼尼齐的方法中,将酚和胺加入到反应器中。通常,快速加入甲醛或其前体,温热以补充该放热反应使反应温度为60-90℃,增加温度低于水的沸点是理想的。否则,水将鼓泡跑掉,引起工艺问题,反应完全后,副产物水可用传统的蒸发方式除去,抽真空、鼓气泡、加热等可达到蒸发目的。常在约100~130℃的温度范围内鼓吹氮气,较低或较高的温度也可使用。
铜反应物(C)可为硝酸盐、亚硝酸盐、卤化物、羧酸盐、磷酸盐、亚磷酸盐、硫酸盐、亚硫酸盐、碳酸盐、硼酸盐、氢氧化物或氧化物。这些包括Cu(Ⅰ)和Cu(Ⅱ)试剂,用作铜反应物(C)的铜化合物包括丙酸铜、醋酸铜,偏硼酸铜、苯甲酸铜、甲酸铜、月桂酸铜、亚硝酸铜、氯氧化铜、棕榈酸铜、水杨酸铜、碳酸铜和环烷酸铜。碳酸铜是最理想的。
本发明的芳族曼尼齐络合物是通过反应制成的。仅将芳香曼尼齐反应物(A)或芳香曼尼齐(B)(Ⅰ)和(B)(Ⅱ)与铜反应物(C)在所需的温度下混合就可实现该反应。该反应也可在至少约80℃下进行。有些情况,该反应也可在低至室温(如约20℃)进行。该反应温度的上限是反应混合物的分解温度(尽管大于250℃几乎是不必要的)。在一具体实例中,该反应温度不超过125℃,不超过115℃更好,优选不超过100℃,不超过90℃最好。
该反应最好在反应物可溶或产物可溶的稀释剂或溶剂中进行。该溶剂可为任何流体惰性溶剂如苯、二甲苯、甲苯、煤油、矿物油、氯苯、二恶烷等。
在一具体实例中,该反应是在芳香烃溶剂中进行的,一旦反应完全或基本完成,加入至少一种有效数量的醇于产物混合物中以防止粘性物质与产物混合物的分离。可使用1-约18个碳原子的醇,在一具体实例中,使用的为异辛醇。芳香烃溶剂与醇的重量比约为5∶1-0.5∶1,约3∶1-1∶1更好,约2∶1最好。
组份(A)、(B)(Ⅰ)、B(Ⅱ)和(C)的相对数量在宽范围内变动。组份(A)的克分子与组份(C)中铜的克原子比以约1.5∶1-3∶1为好,约2∶1-2.5∶1更好,约2.2∶1最好。(B)(Ⅰ)与(B)(Ⅱ)的摩尔比以约2∶1-3∶1为好,约2.4∶1-2.6∶1更好,约2.50∶1-2.55∶1最好。组份(B)(Ⅰ)和(B)(Ⅱ)混合物的克分子与组份(C)中铜的克原子比以2∶1-3∶1为好,约2.2∶1-2.8∶1更好,优选为2.4∶1-2.6∶1,约2.50∶1-2.58∶1最好。
由组份(A)与组份(C)或组份(B)(Ⅰ)和(B)(Ⅱ)与组份(C)反应获得的产物为“有机铜络合物”,即人们认为这是组份(A)的官能团与组分(C)中的金属或组份(B)(Ⅰ)和(B)(Ⅱ)的官能团与组份(C)中的金属通过金属的副价结合而成的。该有机铜络合物的确切本质现在还不为人所知。就本发明的意图来说,这样的络合物在柴油机燃料中应充分稳定,应用于装有排气系统颗粒收集器的柴油发动机中可降低收集于收集器中废气颗粒的引燃温度,这是很必要的。
下列例子说明了有机铜络合物的制备。这些络合物依照本发明而被使用。除特别注明外,下列实例以及整个说明和所附的权利要求,所有材料的量和百分数均以重量计,所有压力为大气压,所有温度为摄氏度。scfh为标准立方英尺/小时。
实施例1
A部分:
在装有脱水器的反应器中,将530g(2.0摩尔)的对四聚丙烯苯酚,700g(2.0摩尔)的N-油基-1,3-二氨基丙烷,66g(2.0摩尔)的多聚甲醛和700ml的甲苯的混合物在100-120℃回流加热3小时。45ml的水被收集在脱水器中,在20mm绝对汞柱压力120℃温度下汽提该混合物。然后,在预成形的50克硅藻土助滤剂填料上过滤该混合物,得到1220g的所需产品。该产品呈浅棕色油状。
B部分:
在装有脱水器的反应器中,将1590g(6.0摩尔)的对四聚丙烯苯酚,183g(3.0摩尔)的一乙醇胺,198g(6.0摩尔)的多聚甲醛和800ml的甲苯的混合物在100-120℃回流加热3小时。122ml的水被收集于脱水器中。在20mm绝对汞柱压力120℃温度下汽提混合物,得到所需产品。该产品呈浅黄色粘性油状。
C部分
在装有脱水器的反应器中,将141g(0.227摩尔)源于A部分的产品,55g(0.089摩尔)源于B部分的产品和100ml的SC-100溶剂(Ohio溶剂产品,相当于芳香烃溶剂)的混合物在搅拌下加热到40-50℃。搅拌下将13.7g(0.124摩尔)的Cu2CO3(OH)2加入到混合物中,加热该混合物至100℃,维持该温度1.5-2小时,直至清绿色混合物形成。少量的水被收集于脱水器中。在20-40mm绝对汞柱压力90-100℃温度下搅拌加热该混合物1小时。1.9ml的水被收集在脱水器中。加入10g硅藻土助滤剂于混合物中并搅拌0.5小时。将混合物的温度降至60℃。在一预成形的20g硅藻土助滤剂填料上过滤该混合物,得190g产品。该产品呈深绿色油状。含铜量为3.0%(重量百分比)。
实施例2
在一反应器中,将75.11g(0.5摩尔)的对叔丁基酚,143.06g(0.51摩尔)的油胺和75ml甲苯的混合物加热到70℃。将17.44g(0.535摩尔)的多聚甲醛加入到混合物中。将混合物加热到90℃。维持回流条件1小时。然后将反应器装上脱水器,混合物维持回流条件1小时。以0.25scfh的速度向混合物中吹进氮气,维持回流条件2小时。10.92g的水被收集于脱水器中。将混合物冷却到60℃,移去脱水器。向混合物中加入25.08g(0.227摩尔)的Cu2CO3(OH)2。向混合物中滴加10.0ml氢氧化铵,10分钟内加完。将混合物加热到90℃,维持回流条件1小时。将反应器上重新加装脱水器,混合物在回流条件下加热1小时,12.8g的水被收集于脱水器中。混合物的温度升高至145℃,50.8g的甲苯从混合物中馏出。向混合物中加入111.94g的SC-100溶剂。用布过滤混合物得所需产品。该产品铜含量为3.68%(重量百分数)。
实施例3
在一反应器,将75.11g(0.5摩尔)的对叔丁基酚,143.06g(0.51摩尔)的油胺和134.6g的SC-100溶剂加热到70℃。向混合物中加入17.44g(0.535摩尔)的多聚甲醛。加热该混合物至80℃,抽真空到充分的真空度以使混合物在80℃回流。混合物维持该回流条件1小时。然后在反应器上加装脱水器,混合物再维持先前的回流条件1小时。向混合物中吹进氮气,维持先前的回流条件2个多小时。8.5g的水被收集于脱水器中。将混合物冷却到60℃,移去脱水器。向混合物中加入25.08g(0.227摩尔)的Cu2CO3(OH)2。向混合物中滴加10ml的氢氧化铵,10分钟内加完。调节合适的真空度使混合物在80℃维持回流1小时。将反应器再装上脱水器,在回流条件下加热混合物3小时。9g的水被收集于脱水器中。混合物的温度升至130℃。冷却混合物到室温。用布过滤混合物得到所需产品。该产品铜含量为4.86%(重量百分数)。
实施例4
在一反应器中,将75.11g(0.5摩尔)的对叔丁基酚,143.06g(0.51摩尔)的油胺和80g的SC-100溶剂的混合物加热到70℃。向混合物中加入17.44g(0.535摩尔)的多聚甲醛。加热该混合物至80℃。抽真空到充分的真空度以使混合物在70℃回流。混合物维持该回流条件1小时。然后将反应器装上脱水器,维持上面的回流条件2小时。以0.25scfh的速度向混合物中吹进氮气,维持上面的回流条件1小时,7g的水被收集于脱水器中。冷却该混合物至60℃,移去脱水器。向混合物中加入25.08g(0.227摩尔)的Cu2CO3(OH)2。向混合物中滴加10.0ml的氢氧化铵,10分钟内加完。调节足够的真空度使混合物在75℃回流,维持这样的回流条件1小时。将反应器重新装上脱水器。该混合物在减压75℃下回流2小时。1g的水被收集于脱水器中。冷却该混合物至室温,向混合物中加入35.42g的SC-100溶剂和58.71g的异辛醇。用布过滤混合物得340.4g的所需产品。该产品的铜含量为3.89%(重量百分数)。
实施例5
在一反应器中,将75.11g(0.5摩尔)的对叔丁基酚,143.06g(0.51摩尔)的油胺和80g的SC-100溶剂加热到70℃。向混合物中加入17.44g(0.535摩尔)的多聚甲醛,加热该混合物至75℃。充分减压以使混合物在80℃回流。维持该回流条件1小时,然后将反应器装上脱水器,混合物维持上面的回流条件2小时。以0.25scfh的速率吹入氮气,并维持上述回流条件1小时。1g的水被收集于脱水器中。冷却该混合物至60℃,移去脱水器。向混合物中加入25.08g(0.227摩尔)的Cu2CO3(OH)2。向混合物中滴加10ml的氢氧化铵,10分钟内加完。调节足够的真空度使混合物在80℃回流。混合物维持该回流条件1小时。将反应器重新装上脱水器,温度升至115℃2小时。5g的水被收集于脱水器中。第1小时后,向混合物中吹进氮气,冷却至室温。向混合物中加入35.42g SC-100溶剂和58.71g异辛醇,用布过滤混合物得364.69g所需产品。该产品铜含量为3.63%(重量百分比)。
本发明柴油机燃料很有用,可作为任何柴油机燃料。在一具体实例中,该柴油机燃料硫含量不超过0.1%(重量百分比),最好不超过0.05%(重量百分比)。硫含量的测定是按照ASTM D2622-87中题为“X-射线光谱测定石油制品中硫含量的标准测定法”中所确定的方法进行的。适于柴油机型发动机使用的有一定沸程和粘度的任何燃料均可使用。这些燃料在约300-390℃的温度范围内,更好地在约330-350℃的范围内典型地具有90%的点蒸馏温度。这些燃料的粘度在40℃时约为1.3-24厘沲。这些柴油机燃料可以按ASTM D975中题为“柴油机燃料油的标准规范”所确定的等级划分为1-D、2-D或4-D级。这些柴油机燃料可含有醇和酯。
本发明柴油机燃料组合物包含一种或多种有效量的上面描述的有机铜络合物,该络合物可降低柴油机燃料燃烧形成的废气颗粒的引燃温度。本发明柴油机燃料的有机铜浓度通常可根据络合物中加合铜的水平来表示。这些柴机机燃料每一百万份包含1-约5000份铜为宜,每一百万份包含1-约500份铜更好,每一百万份包含1-约100份铜最好。在一具体实例中,本发明柴油机燃料每一百万份包含约10-50份的铜,每一百万份包含约20-40份铜更好,每一百万份包含约30份铜最好。
本发明柴油机燃料组合物除了上述有机铜络合物外,还包含为本领域普通技术人员所熟知的其它添加剂。这些添加剂包括抗氧化剂、染料、十六烷值改进剂、防锈剂如烷基化琥珀酸和酸酐、三烷基胺、抑菌剂,阻胶剂、金属减活剂、破乳剂、上部气缸润滑剂和防冻剂。
这些柴油机燃料组合物可与无灰分散剂结合使用。合适的无灰分散剂包括一醇或多醇酯和高分子量单羧酸或多羧酸的酰化剂(酰基部分至少包含约30个碳原子),这样的酯为本领域普通技术人员所熟知。参见例如法国专利1,396,645;英国专利981,850;1,055,337和1,306,529;美国专利3,255,108;3,311,558;3,331,776;3,346,354;3,522,179;3,579,450;3,542,680;3,381,022;3,639,242;3,697,428和3,708,522。这些专利引入本文供参考其合适的酯及制备方法的公开部分。当使用这样的分散剂时,上面所说的有机铜络合物与上述无灰分散剂的比例可以在约0.1∶1-10∶1之间,约1∶1-10∶1更好。
本发明有机铜络合物可以直接加入到燃料中,或者它们可用大量惰性的、普通的液态有机稀释剂(如粗汽油、苯、甲苯、二甲苯或普通液态燃料)稀释形成加合浓缩物。一般地这些浓缩物包含约1%-90%(重量百分数)本发明的有机铜络合物。在一具体实例中,这些浓缩物铜含量约为0.5%-10%(重量百分数),约1%-7%(重量百分数)为好,约2%-6%(重量百分数)更好,约3%-4%(重量百分数)最好。这些浓缩物也可包含一种或多种其它本领域已知的或上述的普通添加剂。
在本发明一具体实例中,有机铜络合物可直接加入或作为上述浓缩物的一部分与柴油机燃料结合使用。该柴油机燃料可用于启动装有排气系统颗粒收集器的柴油发动机。含有机铜络合物的这种柴油机燃料可装入燃料箱中,传输到柴油发动机中燃烧。有机铜络合物可降低排气系统颗粒收集器收集的废气颗粒的引燃温度。
在另一具体实例中,除了由柴油发动机(如汽车、公共汽车、卡车等)驱动的车辆使用有机铜络合物外,也使用了上述操作步骤。该柴油发动机除了使用柴油机燃料外还有一分离的燃料添加剂分配器。柴油发动机运行期间有机铜络合物与柴油机燃料结合或混合。在该实例后部分,燃料添加剂分配器中的有机铜络合物可形成上述讨论的燃料添加剂浓缩物的一部分。柴油发动机运行期间,该浓缩物与柴油机燃料结合。
为示范本发明,提供下列柴油机燃料配方。下列柴油机燃料配方使用了含0.05%(重量百分数)硫的2-D级柴油机燃料。上述例子中使用了有机铜络合物。有机铜络合物的处理水平以一百万份燃料中所加入的铜的分数(ppm)表示。其余的为上述低硫柴油机燃料,用重量百分数表示:
燃料配方 实例 铜(ppm) 柴油机燃料(Wt%)
F-1 1 30 99.9000
F-2 2 30 99.9223
F-3 3 30 99.9383
F-4 4 30 99.9229
F-5 5 30 99.9174
尽管用优选的具体实例解释了本发明,但是实例的许多改良对那些在这方面很熟练的、看到该说明的人来说是很明显的。这可以理解。因此,这里公开的发明应包括这种改良。这种改良在所附权利要求的范围之内。这也是可以理解的。
Claims (10)
1、含有至少一种含铜络合物的组合物,该含铜络合物由组份(A)或组份(B)与组分(C)反应而得,
组分(A)至少是如下结构式
表示的一种化合物,式中R1为1-约6个碳原子的烷基,R2为约16-20个碳原子的饱和或不饱和的脂肪族烃基,
组份(B)是(B)(Ⅰ)和(B)(Ⅱ)的混合物,组份(B)(Ⅰ)至少是一种由如下结构式
表示的化合物,式中R3为约9-18个碳原子的烷基,R4为1-约4个碳原子的亚烷基,R5为约16-20个碳原子的饱和或不饱和的脂肪族烃基,组份(B)(Ⅱ)至少是一种由如下结构式
表示的一种化合物,R6和R8为约9-18个碳原子的烷基,这两个烷基互不相关,R7为1-约4个碳原子的亚烷基,
组份(C)至少为一铜反应物。
2、权利要求1所述组合物,其中R1为叔丁基,R2为油基;R3约有12个碳原子;R4为亚丙基;R5为油基;R6和R8各约有12个碳原子;R7有约2个或3个碳原子;组份(C)为碳酸铜,组份(A)的克分子与组分(C)中铜的克原子之比约为1.5∶1-3∶1;(B)(Ⅰ)与(B)(Ⅱ)的摩尔比约2∶1-3∶1;(B)(Ⅰ)和(B)(Ⅱ)混合物的总克分子与组份(C)中铜的克原子之比约为2∶1-3∶1。
5、含有普通液体有机稀释剂和约1%-90%(重量)权利要求1-4中任一项所述组合物的浓缩物。
6、含有普通液体有机稀释剂和权利要求1-4中任一项所述组合物的浓缩物,该浓缩物的铜含量约为0.5%-10%(重量百分数)。
7、含较多量的柴油机燃料和少量的具有改性性质的、权利要求1-4中任一项所述组合物的柴油机燃料。
8、含较多量的柴油机燃料和少量的具有改性性质的、权利要求1-4中任一项所述组合物的柴油机燃料组合物,该柴油机燃料硫含量不大于约0.05%(重量百分数)。
9、装有排气系统颗粒收集器(以减少收集器收集的废气颗粒的形成)的柴油发动机运行方法,该方法包括用含有效数量的、权利要求1-4中任一项所述的降低收集器中收集的废气颗粒引燃温度的组合物的柴油机燃料使柴油发动机运行。
10、由柴油发动机驱动的、装有燃料添加剂分配器和排气系统颗粒收集器的车辆运行方法,该方法包括使用柴油机燃料使发动机运行;燃料添加剂分配器中使用燃料添加剂,该添加剂包括权利要求1-4中任一项所述的组合物;将有效数量的燃料添加剂与柴油机燃料混合以降低收集于收集器中的废气颗粒引燃温度。
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US5279627A (en) * | 1992-11-06 | 1994-01-18 | The Lubrizol Corporation | Copper-containing aromatic mannich complexes and concentrates and diesel fuels containing same |
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SU794015A1 (ru) * | 1979-01-15 | 1981-01-07 | Московский Ордена Трудового Красногознамени Институт Нефтехимическойи Газовой Промышленности Им.И.M.Губкина | Хелатные аквакомплексы бис-/2-диэ-ТилАМиНОМЕТил-3,4,6-АлКил(циКлОпЕН-TEH-2-ил)фЕНОл/МЕдь/11/ KAK АНТиОКиС-лиТЕльНыЕ пРиСАдКи K СиНТЕТичЕСКиМСМАзОчНыМ МАСлАМ СлОжНОэфиРНОгО ТипА |
GB2056482A (en) * | 1979-08-13 | 1981-03-18 | Exxon Research Engineering Co | Lubricating oil compositions |
FR2470155A1 (fr) * | 1979-11-19 | 1981-05-29 | Lubrizol Corp | Compositions contenant des sels et complexes de metaux ou de metalloides d'aminophenols alcoyles et lubrifiant les contenant |
US4505718A (en) * | 1981-01-22 | 1985-03-19 | The Lubrizol Corporation | Organo transition metal salt/ashless detergent-dispersant combinations |
IN163431B (zh) * | 1982-03-12 | 1988-09-24 | Lubrizol Corp | |
WO1985001513A1 (en) * | 1983-10-05 | 1985-04-11 | The Lubrizol Corporation | Manganese and copper containing compositions |
US4552677A (en) * | 1984-01-16 | 1985-11-12 | The Lubrizol Corporation | Copper salts of succinic anhydride derivatives |
ATE51861T1 (de) * | 1984-11-13 | 1990-04-15 | Mobil Oil Corp | Mannich-basen als oelzusaetze. |
US4655037A (en) * | 1984-12-24 | 1987-04-07 | Ford Motor Company | Carbon ignition temperature depressing agent and method of regenerating an automotive particulate trap utilizing said agent |
CA1260005A (en) * | 1985-09-24 | 1989-09-26 | Frederick W. Koch | Metal complexes of mannich bases |
US4673412A (en) * | 1985-09-24 | 1987-06-16 | The Lubrizol Corporation | Fuel additive comprising a metal compound and an oxime and fuel compositions containing same |
US4828733A (en) * | 1986-04-18 | 1989-05-09 | Mobil Oil Corporation | Copper salts of hindered phenolic carboxylates and lubricants and fuels containing same |
US4749468A (en) * | 1986-09-05 | 1988-06-07 | Betz Laboratories, Inc. | Methods for deactivating copper in hydrocarbon fluids |
JPH02504645A (ja) * | 1986-10-02 | 1990-12-27 | ザ ルブリゾル コーポレーション | チタン錯体およびジルコニウム錯体,および燃料組成物 |
GB2248068A (en) * | 1990-09-21 | 1992-03-25 | Exxon Chemical Patents Inc | Oil compositions and novel additives |
IL100669A0 (en) * | 1991-05-13 | 1992-09-06 | Lubrizol Corp | Low-sulfur diesel fuel containing organometallic complexes |
US5279627A (en) * | 1992-11-06 | 1994-01-18 | The Lubrizol Corporation | Copper-containing aromatic mannich complexes and concentrates and diesel fuels containing same |
-
1992
- 1992-11-06 US US07/973,135 patent/US5279627A/en not_active Expired - Fee Related
-
1993
- 1993-08-25 TW TW82106867A patent/TW292309B/zh not_active IP Right Cessation
- 1993-10-22 BR BR9304048A patent/BR9304048A/pt not_active Application Discontinuation
- 1993-10-26 MX MX9306641A patent/MX9306641A/es not_active IP Right Cessation
- 1993-10-26 US US08/143,320 patent/US5348559A/en not_active Expired - Fee Related
- 1993-10-29 AU AU50377/93A patent/AU660378B2/en not_active Ceased
- 1993-11-03 CA CA002102331A patent/CA2102331A1/en not_active Abandoned
- 1993-11-04 EP EP93117914A patent/EP0596499B1/en not_active Expired - Lifetime
- 1993-11-04 IL IL10748593A patent/IL107485A0/xx unknown
- 1993-11-04 ES ES93117914T patent/ES2106248T3/es not_active Expired - Lifetime
- 1993-11-04 SG SG1996003677A patent/SG64320A1/en unknown
- 1993-11-04 DE DE69311785T patent/DE69311785T2/de not_active Expired - Fee Related
- 1993-11-05 CN CN93114211A patent/CN1044916C/zh not_active Expired - Fee Related
- 1993-11-05 ZA ZA938269A patent/ZA938269B/xx unknown
- 1993-11-05 JP JP5276641A patent/JPH06212176A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE69311785T2 (de) | 1998-01-02 |
DE69311785D1 (de) | 1997-07-31 |
SG64320A1 (en) | 1999-04-27 |
EP0596499B1 (en) | 1997-06-25 |
EP0596499A1 (en) | 1994-05-11 |
CA2102331A1 (en) | 1994-05-07 |
ZA938269B (en) | 1994-06-08 |
JPH06212176A (ja) | 1994-08-02 |
CN1044916C (zh) | 1999-09-01 |
TW292309B (en) | 1996-12-01 |
MX9306641A (es) | 1994-05-31 |
BR9304048A (pt) | 1994-05-10 |
AU660378B2 (en) | 1995-06-22 |
ES2106248T3 (es) | 1997-11-01 |
AU5037793A (en) | 1994-05-19 |
IL107485A0 (en) | 1994-02-27 |
US5279627A (en) | 1994-01-18 |
US5348559A (en) | 1994-09-20 |
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