CN103509611B - A kind of biofuel and preparation method thereof - Google Patents
A kind of biofuel and preparation method thereof Download PDFInfo
- Publication number
- CN103509611B CN103509611B CN201210200197.4A CN201210200197A CN103509611B CN 103509611 B CN103509611 B CN 103509611B CN 201210200197 A CN201210200197 A CN 201210200197A CN 103509611 B CN103509611 B CN 103509611B
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- CN
- China
- Prior art keywords
- biofuel
- weight part
- emulsifying agent
- methyl alcohol
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002551 biofuel Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 296
- 230000000996 additive effect Effects 0.000 claims abstract description 59
- 239000000446 fuel Substances 0.000 claims abstract description 59
- 239000000654 additive Substances 0.000 claims abstract description 58
- -1 isooctyl Chemical group 0.000 claims abstract description 50
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 50
- 150000002148 esters Chemical class 0.000 claims abstract description 31
- 239000003208 petroleum Substances 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 241000158728 Meliaceae Species 0.000 claims abstract description 27
- 239000011734 sodium Substances 0.000 claims abstract description 27
- 229910052788 barium Inorganic materials 0.000 claims abstract description 26
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 21
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims abstract description 18
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000003112 inhibitor Substances 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000005642 Oleic acid Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 26
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 25
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 25
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 25
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 25
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 25
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 239000000872 buffer Substances 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 229960002317 succinimide Drugs 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000002815 homogeneous catalyst Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 abstract description 72
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 40
- 239000000047 product Substances 0.000 description 29
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000013461 design Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 239000000295 fuel oil Substances 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 238000004945 emulsification Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 229920001214 Polysorbate 60 Polymers 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 3
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- HLYOOCIMLHNMOG-UHFFFAOYSA-N cyclohexyl nitrate Chemical compound [O-][N+](=O)OC1CCCCC1 HLYOOCIMLHNMOG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229940082615 organic nitrates used in cardiac disease Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a kind of biofuel and preparation method thereof, this biofuel comprises methanol-based fuel, additive and conventional fossil diesel fuel; The pH value that additive is combined by petroleum sodium sulfonate and barium mahogany sulfonate cushion to, isopropylcarbinol, tritolyl phosphate, methylcarbonate, organic solvent, isooctyl ester nitrate, help emulsifying dispersant and antioxidant formulated by certain processing method.Have according to the biofuel obtained by method of the present invention that cetane value is high, flash-point is high and corrodibility is low, discharge low and that cost is low advantage, alternative common diesel is used for the field such as boiler, car and boat, and effects of energy saving and emission reduction is remarkable.
Description
Technical field
The present invention relates to the technical field of oil fuel, particularly a kind ofly use methyl alcohol, oleic acid, conventional fossil diesel fuel and the additive combination formula preparing biofuel and preparation method thereof.
Background technology
China's oil starvation weak breath, coal resources relative abundance, coal-based alcohol ether fuel source is wide, with advantage alcohol ether substitution of resources or mixing petroleum resources, industry abundant raw materials maturation, comprehensive utilization of resources, be conducive to ecotope, the market requirement is wide, be conducive to industry restructuring, promote the project of sustainable economic development can drive the development of the relevant industries such as the energy, chemical industry and automobile simultaneously, create new growth engines.
The blending technology relative maturity of regular price gasoline, diesel oil, such as, by utilizing some nonstandard condensate oils of refinery after refinement treatment, is aided with additive and can be mixed into the vapour, the diesel oil that meet the requirements of the customers; Such as petroleum naphtha utilizes again, petroleum naphtha octane value is low, RON only has about 40-60, major part was as ethylene cracking material in the past, the blending technology of developed recently is by refining desulfurization and mix with high-octane number component, add octane promoter and can concoct out gasoline, though oil product is not high, can be country and save a considerable number of petroleum resources.
A lot of country once promoted ethanol petrol many years ago, ethanol addition is in the oil generally 10 ~ 15%, cost performance due to ethanol petrol is not winning (such as calorific value obviously reduces), and the main source of ethanol is farm crop, is not the good way of a technical development viewed from market resource; Various countries in recent years equal emphasis turn to pilot conversion methanol gasoline, the market value of methyl alcohol is far below gasoline, main source is the byproduct of Coal Chemical Industry or a lot of chemical industry, present stage technology two tons of coals can produce methyl alcohol more than one ton, production quantity is huge, and do not fight for resource with grain farmer's industry, carbon emission is low during burning, be considered as one of clean fuel substituting or mix oil use by various countries.
Methyl alcohol (CH
3oH) be the simplest compound of structure in lower alcohol, polar hydroxyl groups (OH) in the molecule ratio is very large, and oxygen level, up to 50%, has the advantages that combustionvelocity is fast, heat release is fast, thermo-efficiency is high, and theory joins in gasoline or diesel oil can save petroleum resources in a large number; Methyl alcohol corrodibility is strong, mutually can not mix at normal temperatures, layering can occur with gasoline with arbitrary proportion, upper strata is rich hydrocarbon layers, and lower floor is rich alcohol layer, and therefore methyl alcohol is undesirable at the addition of gasoline present stage, generally≤20%, methanol gasoline market conforming with high-quality requirement is still rare.
The most in short supply on well-known market is diesel oil, the purposes of diesel oil is wide, consumption is large, the demand gap of China's oil fuel is mainly reflected on diesel oil, diesel oil becomes the product in short supply in the energy in short supply, the finished diesel fuel that country every year also wants import a large amount of while imported crude oil, methyl alcohol and diesel oil can be exchanged with the easy application of propellant combination and with fossil diesel fuel and use, be the technology dream of the numerous expert of industry, but not yet better solve so far.Methyl alcohol and diesel oil dissolve each other more difficult, from technology conformation simple analysis, methyl alcohol is typical hydrophilic compounds, can infinitely dissolve each other with water in theory, diesel oil is then the hydrocarbon macromolecular compound of typical oil phase, common saying " water oil is incompatible ", therefore under normal condition, methyl alcohol and diesel oil can not dissolve each other completely, there is several known technical barrier:
One, the compatible problem of methyl alcohol and diesel oil
Methanol hydroxylethyl (OH) in the molecule ratio is very large, in polarity, diesel oil is by the hydro carbons hydrocarbon compound of various many carbon atoms, nonpolar, can only be dissolved in nonpolar solution, methyl alcohol and diesel oil be made stable fused in varing proportions, and do not change its combustioncharacteristics, must by the suitable additive (solubility promoter) of cost performance, current technology generally selects higher alcohols, Viscotrol C and ester compound or its mixture as solubility promoter.
Two, the problem that methanol diesel-oil flash-point is low, cetane value is low
The flash-point of methyl alcohol is low (11-12 DEG C), differs comparatively far away with diesel-fuel flash point (55 DEG C), and after methyl alcohol and diesel oil mixture, low-flash methyl alcohol still can catch fire at low temperatures, and self-igniton engine operating mode instability can be caused also dangerous; Diesel-fuel cetane number requires at 45-49, can reduce cetane value, weaken explosive power, affect engine behaviour after methyl alcohol and diesel oil mixture.Technically add ignition improver at present, improve the flammability of methanol fuel, known ignition improver is similar to diesel cetane-number improver, for organic nitrates ester compound, such as cyclohexyl nitrate, the positive ethyl ester of nitric acid, glycol ether dinitrate, triethylene glycol dinitrate etc.
Three, methanol diesel-oil and emulsifying water lamination problem
Due to polarity methyl alcohol and nonpolar diesel oil immiscible, even if methyl alcohol and the miscible also extremely unstable of diesel oil, the moisture of denier invades and also can cause emulsification layering, generally add a certain amount of emulsifying agent in the solubility promoter of methanol diesel-oil, methyl alcohol is under the existence of emulsifying agent, comparatively stable methyl alcohol microlayer model can be formed and be scattered in emulsion in diesel oil, improve stability and the ignition quality of methyl alcohol/diesel blended fuel, usually use ionic emulsifying agent.
According to open source information, in the M15 methyl alcohol-diesel blended fuel of Germany's test, the volume addition of solubility promoter is 15%, and the volume addition of ignition improver is 1%, and the cetane value of fuel can reach 45; And when using methyl alcohol as main fuel, the volume addition of ignition improver is 5%-10%, because the price of solubility promoter and ignition improver is all very high, and consumption is very large, its promoting the use of in the fuel of market of limit value.
Chinese invention patent application (2006101449663.5) discloses a kind of methanol modifier, its lubricant is oleic acid, ignition dope is butylacetate, priming mixture is sherwood oil, dewatering agent is polyoxyethylene nonylphenol ether, anti-wear agent is clorafin, oxidation inhibitor is 2,6 ditertiary butyl p cresol, sanitising agent is zellon, sanitas is benzotriazole, cetane number improver is isooctyl ester nitrate, phase solvent is propyl carbinol, octanol or its mixture.A kind of methanol diesel-oil is disclosed in another part of Chinese invention patent application (201010274919.1), the hydrophile-lipophile balance value of its tensio-active agent is 3 ~ 6, adopt non-ionic polyoxyethylene ethers fluorine carbon, lipid acid mountain jasmine smooth, poly-mountain jasmine ester, alkylphenol polyoxyethylene etc., cosurfactant adopts propyl carbinol, n-Octanol, n-dodecanol etc., and auxiliary agent comprises oleic acid, alkyl phenol sulfonate, dialkoxy zinc dithiocarbamate, dioxy base silicone oil, isooctyl ester nitrate, the luxuriant ferrocene of ring, thanomin etc.These formulas contribute to dissolving each other of methyl alcohol-diesel oil all to a certain extent, also all there is mutual solubility deficiency, easily layering, clarity is not enough, or the defect of cost performance aspect.
Much be mainly derived from vegeto-animal industrial organism, can stable, safe and reliable, the much higher first composite fuel oil of fuel value of forming property by the additive of specific combination, its proterties is similar to conventional fossil diesel fuel, but there is the feature of low-carbon (LC) or abrasive burning and exhausting, both can be added into conventional fossil diesel fuel to use as auxiliary material, also can starting material master, the easy bit map of supporting role, in recent years forward position research and development custom is this kind of multiple elements design oil fuel and be commonly referred to as biofuel with the blended fuel of conventional fossil diesel fuel, and the present patent application has continued to use this agreement title.
Summary of the invention
The object of the invention is to: disclose combination formula of a kind of biofuel and preparation method thereof, general industry methyl alcohol, oleic acid or carbinol-modified complex body are dissolved each other by the additive of specific combination is stable, used in combination by a certain percentage with conventional fossil diesel fuel, use as " biofuel " with low-carbon (LC) or abrasive feature, to scheme to save petroleum resources largely, reach the technology application target of energy-saving and emission-reduction.
For achieving the above object, the invention provides combination formula of a kind of biofuel and preparation method thereof, biofuel is dissolved each other by methanol-based fuel and combined additive and conventional fossil diesel fuel and is formed, and it is characterized in that, based on the biofuel of 100 weight parts, comprising:
Methanol-based fuel 27 ~ 96 weight part is the mixture of methyl alcohol and oleic acid, or the mixture of methyl alcohol and carbinol-modified complex body, or carbinol-modified complex body; Carbinol-modified complex body described herein, at least comprise in following material one or more: having general formula is ROCH
3ethers (ethers of methyl alcohol and alcohol condensation) and to have general formula be RCOOCH
3ester class (the ester class of methyl alcohol and sour condensation);
Common diesel 0 ~ 70 weight part, is common petrifaction diesel, comprises the models such as 10#, 0# ,-10# ,-20# ,-35#, 10#, 20#, 30#;
Additive is 2 ~ 8 weight parts, and based on the additive of 100 weight parts, it has following composition;
Emulsifying agent 15 ~ 25 weight part;
PH value buffer reagent 20 ~ 33 weight part;
Tritolyl phosphate 8 ~ 12 weight part;
Isooctyl ester nitrate 4 ~ 8 weight part;
Help emulsifying dispersant 0.7 ~ 3 weight part;
Oxidation inhibitor 0.35 ~ 2 weight part;
Isopropylcarbinol 18 ~ 30 weight part;
Organic solvent 13 ~ 20 weight part;
Described methanol-based fuel, when it is methyl alcohol-oleic acid mixture, or during the mixture of methyl alcohol and carbinol-modified complex body, methyl alcohol 2 in the mixture weight accounting is 10 ~ 90%.
Respectively will to form biofuel below and function is introduced.
Oleic acid (chemical skeleton symbol CH
3(CH
2)
7cH=CH (CH
2)
7cOOH) being the unsaturated fatty acids containing 18 carbon atoms and 1 double bond, is a kind of important component forming animal and plant grease, water insoluble; Oleic acid has served as extremely important role in the modification of methyl alcohol, both can as emulsifying agent, again by the carbinol-modified multipolymer for " lipophilicity " liquid biological fuel, (content range lower limit segment is got) when oleic acid addition is less, oleic acid act as partial emulsifier role in oil fuel, Main Function jointly helps methyl alcohol to reach microemulsified with Span series and TWEEN Series (or OP-10), make other component in additive more uniformly be dispersed in carbinol-modified system, reach the object promoting fuel value; And when its addition is larger, the Main Function that oleic acid rises is used to " modification " methyl alcohol, and improve the combustion heat of methyl alcohol.
Described emulsifying agent, it act as and makes the solvent of methyl alcohol and little polarity form uniform emulsion, for the present invention, use common emulsifying agent namely can play the effect of emulsification, be preferably the composite mixture of Span series (Span) emulsifying agent and TWEEN Series (TWEEN) emulsifying agent, or the composite mixture of Span series emulsifying agent and OP-10 emulsifying agent.Sapn emulsifying agent is the ester that anhydrous sorbitol and higher fatty acid condensation are formed, be dissolved in methyl alcohol, hydrophile-lipophile balance value (HLB) 4.7, it is a kind of desirable w/o type emulsifying agent, there is very strong emulsification, dispersion, lubrication, can be mixed with all kinds of emulsifying agent, especially the effect of composite use is better with tween emulsifier, preferably uses Arlacel-80 (SP-80) for the present invention.Tween emulsifier is the condenses (polyoxyethylene sorbitan fatty acid ester) of sapn and oxyethane, and point T-20, T-40, T-60, T-80 etc. are multiple, for preferred TWEEN-80 and TWEEN-60 of the present invention and the composite use of Span series emulsifying agent.Emulsifier op-10 is the mixture of alkylphenol polyoxyethylene, belongs to nonionic surface active agent, and have emulsification, wetting, diffusion, the premium propertiess such as antistatic property, the emulsifying agent composite with Span series has good protection effect to Emulsification of Fuel Oil system.Span series emulsifying agent and TWEEN Series (or OP-10) emulsifying agent is composite when using, the part by weight of Span series emulsifying agent and TWEEN Series (or OP-10) is preferably 2:1 ~ 4:1, be more preferably 2.5:1 ~ 3.5:1, make mixture can form desirable w/o type microstructure.
The stability acting as the pH value of maintenance system of pH value buffer reagent, available pH buffer reagent must have following feature: be dissolved in organic solvent, and preferably liquid, corrosion-free to engine, and the stability of methyl alcohol-oil phase emulsification system can not be destroyed, have certain surge capability, all there is this feature compound or its combination all go for pH buffer reagent.For the present invention, be preferably the combination of barium mahogany sulfonate and petroleum sodium sulfonate.Barium mahogany sulfonate (T701) and petroleum sodium sulfonate (T702) are the known rust preventive for metal surface of industry, the sulfonic group of a strongly hydrophilic and alkyl is had to be linked in molecular structure, the pH value of the sulfuric acid of these two kinds of high fatty alcohols is 7-8, but due to common-ion effcet under solution state, the reversible quality of balance of dissociation is different, the pH value buffering that formation capable of being combined is desirable under enough concentration and suitable proportion is right, and the petroleum sodium sulfonate in solution is antacid composition, barium mahogany sulfonate is alkali resistant composition; Its buffering conjugation conformation model is: petroleum sodium sulfonate (R-SO
2o
-na
+) dissociation degree comparatively strong, under solution state, whole dissociation goes out Na
+and SO
2o
-; Barium mahogany sulfonate (R-SO
2o
-ba
++oSO
2-R) dissociation degree relatively weak, be in structure in the solution and dissociate trend, mainly with R-SO
3ba
+and SO
2o
-form exist, Na in buffer reagent
+and SO
3h
-dissociation concentration larger; When the miscible system of oil fuel causes free state H because absorbing the oxidated factor such as occur becoming sour of carbonic acid gas in air, ester class
+when total amount increases, SO
3h
-can and system in H
+in conjunction with formation mahogany acid; Otherwise, when the miscible system of oil fuel to be decomposed because of amination salt that internal composition is residual or other factors causes OH
-time more than needed, Na
+can the interior free OH of inhibition system
-and other negatively charged ion, thus make the acid base equilibrium degree of oil fuel buffered soln be in the right conjugation protection domain of buffering, make the miscible system of oil fuel keep stable.
When completing biofuel mixture, what should be noted adjustment product contains acid number, petroleum products represents the summation of acidic substance usually by acidity, the perishable parts of the diesel oil that acidity is large, and coking and the incrustation of oil nozzle and combustion chamber can be increased, the acidity being not more than 7mgOH/100mL(national regulations diesel oil should be adjusted to).The concrete enforcement of buffer reagent need be determined according to the acidity of concocted main fuel source (intermediate), the buffer content scope that additive of the present invention is demarcated, be applicable to oil fuel or its intermediate of petroleum products mark rule acidity criteria product routinely, described acidity criteria is that rule value marked by potassium hydroxide (mg) in 100mL product He required; But market is used as many intermediate product of oil fuel because of manufacturing process slant acidity, in addition many biofuel blendings often use some substandard petrifaction diesels (to derive from the fractionation of viscous crude, acidity higher genus industry is known), when concocting this kind of fuel oil, be equivalent to and add a certain amount of barium mahogany sulfonate in advance at compound intermediate, should add less according to the actual acidity of blending object and even not add barium mahogany sulfonate, the consumption of corresponding increase petroleum sodium sulfonate.
Tritolyl phosphate, also known as Tritolyl Phosphate, it has multiple isomer, all can be applied to the present invention, and effect is similar, such as T306, molecular formula C
21h
21o
4p, is typically used as softening agent, such as, for increasing the snappiness of paint film in painting, is also used as synthetic rubber, polyester, polyolefine and flame retardant of plastic agent.T306 is dissolved in alcohol, benzene, ether, vegetables oil, the many organic solvents of mineral wet goods, and stability is strong, not volatile, can give the wear resistance that superpolymer is good.Be anti-wear agent at the dominant role of combined additive of the present invention, serve as fire retardant simultaneously, to wear-resistant, fire-retardant, improve flash-point and play multiple action.
Isooctyl ester nitrate (having another name called nitric acid 2-ethylhexyl or isooctyl ester nitrate), except effectively can improving the cetane value of diesel oil/methanol fuel oil/methanol diesel-oil, combustionproperty can also be improved, shorten ignition time, reduce burning-point, improve locomotive thermal condition dynamic property, in composite fuel oil, add the isooctyl ester nitrate of 0.1%-0.3%, generally can improve cetane value 2-9 unit.
Described helps emulsifying dispersant, its function is that the component of this additive is effectively dispersed to concocted biofuel, and minimizing carbon distribution can be played, reduce electrostatic accumulation effect biofuel, prior art has certain research to assistant for emulsifying agent, the emulsifying dispersant that helps of the present invention is selected from one in the derivative series product (such as T154A, T154B, T161A, T161B, T151, T155, T164A, T165A etc.) of succinate, polyolefinic succinimide acid polyhydroxy alkyl ester or polyisobutene, or wherein several combination; Such as T161A be with high-activity polyisobutene (molecular weight is for 2300) be raw material, the high molecular ashless dispersant that adopts hot adduction technique to prepare, there is good cigarette ash, the dispersion of greasy filth and solublization, can effectively suppress fuel oil viscosity to increase.
Methanol fuel oil corrodibility is by force a known technology difficult problem, generally solve by adding corrosion inhibitor, and in oil product, ingredient is oxidized can produce acid, throw out and generation variable color can shorten the quality guaranteed period of oil product, the industrial general method of oil oxidation stability of improving is for employing synthesis type base oil and refining base oil, unstable component in removing oil product, or add oxidation inhibitor, oxidation inhibitor is generally selected from 124 Triazole class (such as T406: 124 Triazole stearylamine salt, TTAS: methyl benzotriazazole sodium salt, N-nonyl oxygen methyl benzotriazole), thiadiazole (such as T561:2, two (alkyl dithio) thiadiazoles of 5-) and sulphur phosphorous antioxygen corrosion inhibitor, this kind of sulfur-bearing, the mainstream product of the oxidation inhibitor of phosphorus is zinc dialkyl dithiophosphate (ZDDP), T504: sulfenyl phenolate etc.
The oxidation inhibitor that the present invention adopts, not only be conceived to weaken to concoct in base fuel and additive formulations some solubility promoter to copper or other corrosion of metal power, some solubility promoter to be weakened in additive formulations to the corrosion strength of rubber simultaneously, and have the advantages that oil soluble is good, reductibility is strong, reach the object effectively improving this combined additive preparation of fuels oil erosion resistance.The oxidation inhibitor that the present invention selects comprises one in following a few class or several combination: amine type oxidation inhibitor (pentanoic that such as N-phenyl-a-naphthylamine or octyl group/butyl mixed alkyl replaces); Phenol type antioxidant, such as T501:2,6-ditertbutylparacresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butyl phenols, T502: mixed type liquid barrier phenol, T5114,4: methylene-bis (2,6-di-tert-butylphenol), T512: phenolic ester type oxidation inhibitor etc.; Phenol amine type oxidation inhibitor, its main products such as 2,6-di-t-butyls-alpha, alpha-dimethyl amido p-cresol; Sulphur phosphorous antioxygen corrosion inhibitor and dialkyl dithiocarbamate, use wherein a kind of or several oxidation inhibitor combination, do not limit relative proportion when combinationally using.
Isopropylcarbinol is typically used as softening agent, synthetic rubber and synthetic drugs etc., is typically used as additive, the effect in additive formulations of the present invention, is not only and plays the part of the organic solvent that hydrotropy helps emulsification, and serve as multiple player in petroleum industry; The combustion heat of such as isopropylcarbinol is 2667.7kJ/mol, boiling point 107 DEG C, can combustion-supporting, the combustion heat that strengthens oil fuel explosive power, improve composite fuel, can improve the clarity of biofuel oil simultaneously, reduce carbon distribution during burning; The combination of isopropylcarbinol and isooctyl ester nitrate, can improve the cetane value of composite fuel significantly.
Isopropylcarbinol also can be considered a kind of composite organic solvent in additive of the present invention, and its components by weight percent is 1:1 ~ 2:1 with the relative weight ratio of described organic solvent; Described organic solvent, comprise in aromatic solvent, ketones solvent, nitro solvent, esters solvent, ether solvent one or more.The compounded combination of isopropylcarbinol and organic solvent, can reduce condensation point and the cold filter clogging temperature of biofuel effectively.
Described organic solvent should have following technical characteristic, and such as fusing point is low, good fluidity, do not destroy emulsification system, non-corrosiveness etc.; When the flash-point of solvent, solvent octane value or cetane value are higher, prepare the additive obtained and there is more advantage.Organic solvent can be selected from aromatic hydrocarbon solvent, ketones solvent, esters solvent, ether solvent and nitro solvent, but does not recommend to select the solvent that may pollute environment, and such as nitro kind solvent may produce the discharge of oxynitride.Aromatic hydrocarbon solvent comprise toluene, dimethylbenzene and other contain the solvent of aromatic ring structure; Ketones solvent comprises acetone, butanone and other ketone compounds; Esters solvent comprises the compounds such as ethyl acetate, methylcarbonate, original methyl carbonate, triethyl orthoformate; Ether solvent then comprises t-butyl methyl ether, glycol dimethyl ether, and other have the ether of ether structure general formula.The organic solvent preferentially selected in the present invention comprises t-butyl methyl ether (MTBE), toluene, TAME(tert amyl methyl ether(TAME)), methylcarbonate (DMC).Such as methylcarbonate (DMC) is that one is nontoxic, environmental-protecting performance is excellent, broad-spectrum industrial chemicals, and containing functional groups such as carbonyl, methyl and methoxyl groups in molecular structure, the advantage as fuel oil additive has extensively been admitted; Toluene is the important source material of organic chemical industry, is used as fuel oil additive in a large number by fuel industry.These organic solvents are regarded as again octane value or cetane number improving agent usually, because the oxygen level in molecular structure and molecule is had nothing in common with each other, respectively have its handling characteristics, but one or more mixtures use.
Additive in the present invention can also improve methanol-based fuel oil flash.Flash-point is the vital critical index of methanol-based oil fuel, because the flash-point of methyl alcohol is low, methanol-based oil fuel is made to reach the flash point requirements of common diesel, one of technology outlet is first by thorough for methyl alcohol modification, make it to promote enough flash-points before combination, such as, methyl alcohol-oleic acid mixture is utilized strong acid or strong base catalyst copolymerization; Two of technology outlet is preferred emulsifiers, generally selects ionogenic surfactant.From conformation model, the microstructure of methyl alcohol-oleic acid or methyl alcohol-diesel oil will desirablely be in a disguised form a kind of microemulsion of complete water-in-oil-type, the i.e. complete zoarium of water-in-oil-type, need to be issued to satisfactory emulsification by the effect of tensio-active agent, accomplish that methyl alcohol does not separate out the zoarium of water-in-oil film formation at flash-point lower limit.Will improve flash-point further, need in formula, strengthen water-in-oil-type incorporation, described tricresol phosphate ester content of such as filling a prescription gets range limit, can play castering action to raising flash-point; Also can on described composite emulsifier basis, more composite to the complete fit specific emulsifying agent of formation water-in-oil film, methanol fuel oil is improved enough flash-points.And selected part to have in strong molecule or the material of intermolecular hydrogen bonding, due between molecule or intramolecular interaction indirectly improve fuel oil flash.
The preparation method of described biofuel, be divided into by formula four class components first fully to mix, and then four class components are mixed into biofuel, process of preparing carries out according to the following steps:
(1), after being dissolved completely in organic solvent by oxidation inhibitor, first kind component is fully mixed with into isooctyl ester nitrate;
(2) by two components in pH value buffer reagent, tritolyl phosphate with help emulsifying dispersant to mix, then be heated to stop after pH value buffer reagent dissolves completely in constantly stirring, be cooled to < 40 DEG C in Keep agitation after, isopropylcarbinol is added and stirs, be prepared into Equations of The Second Kind component;
(3) the 3rd class component is obtained after kind of the component of two in emulsifying agent being mixed;
(4) add the 3rd class component after first kind component being mixed with Equations of The Second Kind component to mix, obtain additive;
(5) additive being joined in methanol-based fuel, by adding petroleum sodium sulfonate or barium mahogany sulfonate makes its acidity be less than 7mg KOH/100mL, obtaining biofuel.
As a kind of Optimization Technology that carbon oil fuel of the present invention is implemented, described methanol-based fuel is got the raw materials ready as follows: add and help mixed gathering with the promoter of oleic acid weight accounting 0.5 ~ 2%, and take off after promoter and dewatering process for subsequent use through ordinary method, the promoter herein used is the catalyzer of esterification, comprise homogeneous catalyst and (comprise liquid strong acid (vitriol oil), such as Lewis acid and salt), solid catalyst (comprises solid acid, solid alkali, metal catalyst, such as tosic acid, sodium hydroxide, heteropolyacid catalyst, Fe-Zn double metal cyanide), the enzyme catalyst that ionic-liquid catalyst and in recent years new development are got up.
Above-mentioned processing method is conducive to mixing and dissolves each other, and when preventing all components from mixing, reaction produces by product simultaneously simultaneously, affects the result of use of additive.Barium mahogany sulfonate usual products when preparing in Equations of The Second Kind component is solid, heats up and contributes to accelerate dissolution; Due to containing oxidation inhibitor in first kind component, be not suitable for heat treatment, and generic xln much planted by the oxidation inhibitor in first kind component, is soluble in organic solvent, therefore add again after being dissolved in organic solvent.Oxidation inhibitor is dissolved completely and adds isooctyl ester nitrate again, be conducive to the abundant dispersion of oxidation inhibitor in first kind component, avoid oxidation inhibitor oxidized thus cause Additive Properties to decline.Feed way of the present invention efficiently avoid the problem of the additive finished product usefulness decline occurred when one kettle way adds material, mixture can be made to form the micro-dispersed texture of desirable water-in-oil-type, effectively avoid the problem of shortened shelf life.In addition, for dissolving the organic solvent of other components, because its Main Function is for dissolving and improving cetane value, it adds order and can be decided according to the actual requirements flexibly and the order of addition(of ingredients) that is not limited to above-mentioned technique.
Hybrid technique method comprise Conventional rotary stir, periodically or the random shearing stirring of corner cut, magnetic swash resonance mixing and negative pressure (< 25Mpa) and help mixed poly-etc., preparation process can be heated hydrotropy.The shearing stirring that described Conventional rotary stirring, periodicity or corner cut are random and pressurization (< 25Mpa) device, all easily commercially purchase; Resonance device is swashed about magnetic, existing in " a kind of liquid energy exciting device " (ZL200410074446.5) of invention patent mandate detailed description in detail has been obtained present invention applicant, this device comprises the liquid treatment chamber (waveguide cavity) with metal or the subsidiary formed material of wire netting, the n of arrangement is replaced to permanent magnet (m >=0.2mm along liquid in-out mouth passage with m spacing in chamber, n >=2), built-in or be configured in cavity there is >=1 tuning-points, can make the physics-chem characteristic such as solubleness, oxygen level, perviousness, the speed of reaction etc. that are subject to processing liquid that larger change occurs.
Use combination formula of the present invention and preparation method thereof, can provide a kind of pervasive biofuel for market: be prepared as " biofuel oil " by additive agent modified by methanol-based fuel, be the ideal substitute of boiler common diesel; Also can follow this technological approaches, become " biofuel compound diesel " with stable the dissolving each other of conventional fossil diesel fuel.Although it should be noted that part of fuel oil can not add conventional fossil diesel fuel in it, its proterties and suitable application area and common fossil diesel fuel do not have difference, therefore are collectively referred to as biofuel herein.
The biofuel that the present invention makes has following several advantages:
1, dynamic property is strong: combined additive is composite improves calorific value, strengthen the several important component of power, the biofuel oil making to make, biofuel leading indicator reach or are better than commercially available 0# diesel oil, cetane value is generally greater than 46, and dynamic property strengthens compared with its like product;
2, carbon discharge capacity is few: combined additive helps the microcapsule structure that oil fuel dissolves each other into oily armored alcohol, makes noxious emission CO, NO during burning
x, HC content obviously reduces, emission smoke intensity fall is more than 70%, environmentally friendly;
3, filter point and condensation point reduce than the same label diesel oil of mixture, can use under low temperature environment;
4, versatility is good: ordinary diesel oil can be replaced directly to use, and can meet requirement and the steady running of engine, has with the finished diesel fuel of same label mixture the scope of application be equal to;
5, applied widely: to be applicable to the various different purposes such as stove, Industrial Stoves and diesel engine locomotive, and without the need to changing diesel motor;
6, stationary phase is long: stationary phase >=6 months, adapt to store, transport and sell time needed for each link.
Embodiment
Embodiment 1,
Prepare a kind of biofuel 1 of abrasive, design conventional 0# diesel oil weight accounting 30% in biofuel, methanol-based oil fuel accounts for 62.9%.Measure 480g methyl alcohol, measure 400g oleic acid and measure conventional 0# diesel oil (purchased from Sinopec) of 420g, additive formulations comprises following component and content:
Arlacel-80 emulsifying agent 18g, OP-10 emulsifying agent 6g;
PH value buffer reagent 20g, wherein petroleum sodium sulfonate 11g, barium mahogany sulfonate 9g; ;
Isopropylcarbinol 21g;
Tritolyl phosphate 11g;
Toluene 13g;
Isooctyl ester nitrate 8g;
Emulsifying dispersant is helped to select the T161A product 1.0g of dimethyl succinate 1.0g, derivatives of poly (iso) butene series to combine;
Antioxidant selects N-phenyl-a-naphthylamine (T531) and 2,6-di-t-butyl-each 0.5g of alpha, alpha-dimethyl amido p-cresol to combine.
Above-mentioned raw materials altogether 100g, be commercially available common raw material, purity is greater than 96%, the raw material of use higher degree be conducive to obtaining the longer quality guaranteed period biofuel.
Preparation method is undertaken by following technique:
(1) methyl alcohol is mixed with oleic acid, be prepared into methanol-based fuel;
(2) antioxidant is dissolved completely in toluene, fully mix with isooctyl ester nitrate, be prepared into first kind component;
(3) by petroleum sodium sulfonate and barium mahogany sulfonate, tritolyl phosphate with after helping emulsifying dispersant to mix, isopropylcarbinol is added and stirs, be prepared into Equations of The Second Kind component;
(4) sapn emulsifying agent and OP-10 are mixed, obtained 3rd class component;
Then, first kind component mixing Equations of The Second Kind component is stirred, add after the 3rd class component mixes, add methanol-based fuel to stir, finally add conventional 0# diesel oil to stir, be less than 7mgKOH/100mL with petroleum sodium sulfonate or barium mahogany sulfonate fine setting to acidity after 10 minutes, namely obtain constitutionally stable biofuel 1 of dissolving each other, it is a yellow transparent liquid, and various parameter is as shown in table 1.
The parameter of the part biological diesel oil that table 1 prepares
1 ton of common No. 0 diesel oil mixture can be that 3.33 tons of biofuel 1 use by the present embodiment, comprehensive cost is low, cetane value reaches 46.1, fire row is high-volume lower than 20% of common No. 0 diesel oil, and the quality guaranteed period reaches 6 months, be a kind of desirable biofuel, valuable fossil energy can be saved in a large number.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 2
Prepare another kind of biofuel, design common diesel weight accounting 70% in biofuel, methanol-based fuel accounts for 27.6%.Measure 738.0g methyl alcohol and the conventional 0# diesel oil of 2075g, oleic acid measures 82.0g, and the composition of additive changes to:
Arlacel-80 emulsifying agent 16g, Tween-60 emulsifying agent 8g;
PH value buffer reagent 18g, wherein petroleum sodium sulfonate 10.0g, barium mahogany sulfonate 8.0g; ;
Isopropylcarbinol 30g;
Tritolyl phosphate 9.95g;
T-butyl methyl ether 13g;
Isooctyl ester nitrate 4g;
Emulsifying dispersant is helped to select the T161A product 0.35g of diethyl succinate 0.35g, derivatives of poly (iso) butene series to combine;
N-phenyl-a-naphthylamine (T531) 0.35g selected by antioxidant.
Preparation process and embodiment 1 are roughly the same.Obtained biofuel is a deep yellow transparent liquid biofuel 2, and its design parameter is in table 1.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 3
Prepare another kind of biofuel, design common diesel weight accounting 40% in biofuel, methanol-based amount of fuel addition is 54%, and measure 60g methyl alcohol and the conventional 0# diesel oil of 400g, oleic acid measures 480g, and binder component is changed into:
Emulsifying agent 20 weight part, wherein SP-80 emulsifying agent 15 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 21 weight part, comprises petroleum sodium sulfonate 11 weight part, barium mahogany sulfonate 10 weight part;
Tritolyl phosphate, 10 weight parts;
Isooctyl ester nitrate, 6 weight parts;
Helping emulsifying dispersant, use the T161A(polyisobutylene succinamide of dimethyl succinate 1.0 weight part, derivatives of poly (iso) butene series) product 1.0 weight part combines;
Oxidation inhibitor, uses N-phenyl-a-naphthylamine (T531) and each 0.5 weight part of 2,6-di-t-butyl alpha, alpha-dimethyl amido p-cresol to combine;
Isopropylcarbinol, 20 weight parts;
Organic solvent 20 weight part, uses toluene 10 weight part and methylcarbonate (DMC) 10 weight part to combine.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 60g additive by embodiment 1, obtained biofuel 3 is a yellow transparent liquid, and its design parameter is in table 1.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 4
Prepare another kind of biofuel, design common diesel weight accounting 44% in biofuel, methanol-based fuel accounts for 50%, and measure 150g methyl alcohol and the conventional 0# diesel oil of 440g, Linolenic acid methylester gets 350.0g, and binder component is changed into:
Emulsifying agent 20 weight part, wherein SP-80 emulsifying agent 15 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 30 weight part, comprises petroleum sodium sulfonate 15 weight part, barium mahogany sulfonate 15 weight part;
Tritolyl phosphate, 9 weight parts;
Isooctyl ester nitrate, 6.2 weight parts;
Help emulsifying dispersant, use two succimide 0.8 weight part, T165A product 1.2 weight part of derivatives of poly (iso) butene series combines, wherein two succimide is also known as two extension, for a kind of oil product dispersion agent of the exploitation sixties in last century, two succimides that the present invention selects are meet the commercially available of SH/T 0623-95 standard to help emulsifying dispersant;
Oxidation inhibitor, uses zinc dialkyl dithiophosphate (ZDDP) 0.5 weight part and 2,6-di-t-butyl alpha, alpha-dimethyl amido p-cresol 0.3 weight part to combine.
Isopropylcarbinol, 19 weight parts;
Organic solvent uses toluene, 13 weight parts.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 60g additive by embodiment 1, obtained biofuel 4 is a yellow transparent liquid, and its design parameter is in table 1.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 5
Prepare another kind of biofuel, design common diesel weight accounting 8% in biofuel, methanol-based fuel accounts for 85%, and measure 300.0g methyl alcohol and the conventional 0# diesel oil of 80g, oleic acid measures 550.0g, and binder component is changed into:
Emulsifying agent 20 weight part, wherein SP-80 emulsifying agent 15 weight part, TWEEN-60 emulsifying agent 5 weight part;
PH value buffer reagent 20 weight part, comprises petroleum sodium sulfonate 10 weight part, barium mahogany sulfonate 10 weight part;
Tritolyl Phosphate, 11 weight parts;
Isooctyl ester nitrate, 6 weight parts;
Help emulsifying dispersant, T155A product 0.8 weight part of use polyolefinic succinimide acid glycol ester 1.2 weight part, derivatives of poly (iso) butene series combines;
Oxidation inhibitor, pentanoic (T534) 0.5 weight part using methyl benzotriazazole sodium salt 0.5 weight part and octyl group/butyl mixed alkyl to replace combines.
Isopropylcarbinol, 22 weight parts;
Organic solvent 18 weight part, uses ethylbenzene 9 weight part and methylcarbonate (DMC) 9 weight part to combine.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 70g additive by embodiment 1, preparation process roughly the same.Obtained biofuel 5 is a yellow transparent liquid.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 6
Prepare another kind of biofuel, design common diesel weight accounting 4% in biofuel, methanol-based fuel accounts for 90%, and measure 300.0g methyl alcohol and the conventional 0# diesel oil of 40g, oleic acid measures 600.0g, and binder component is changed into:
Emulsifying agent 24 weight part, wherein SP-80 emulsifying agent 16 weight part, TWEEN-80 emulsifying agent 8 weight part;
PH value buffer reagent 22 weight part, comprises petroleum sodium sulfonate 12 weight part, barium mahogany sulfonate 10 weight part;
Tritolyl phosphate, 10 weight parts;
Isooctyl ester nitrate, 6 weight parts;
Help emulsifying dispersant, use T161A product 1.0 weight part of derivatives of poly (iso) butene series;
Oxidation inhibitor, uses 2,6-di-t-butyl alpha, alpha-dimethyl amido p-cresol 0.5 weight part.
Isopropylcarbinol, 20 weight parts;
Organic solvent 16.5 weight part, uses toluene 8.5 parts and MTBE 8 parts to combine.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 60g additive by embodiment 1, preparation process roughly the same.Obtained biofuel 6 is a yellow transparent liquid.Use two different east wind comingses 260 to test, test when external temperature-10 DEG C, the number of starts and start time all reach requirement, start success ratio and reach 100%, and exhaust emissions amount meets EPA2002 and EPA2007 standard.
Embodiment 7
Prepare another kind of biofuel, design common diesel weight accounting 2% in biofuel, methanol-based fuel accounting 96%, measure 300.0g methyl alcohol and the conventional 0# diesel oil of 20g, oleic acid measures 660.0g, and binder component is changed into:
Emulsifying agent 15 weight part, wherein SP-80 emulsifying agent 10 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 33 weight part, comprises petroleum sodium sulfonate 25 weight part, barium mahogany sulfonate 8 weight part;
Tritolyl phosphate, 10 weight parts;
Isooctyl ester nitrate, 6 weight parts;
Help emulsifying dispersant, T165A product 1.2 weight part of use dimethyl succinate 0.8 weight part, derivatives of poly (iso) butene series combines;
Oxidation inhibitor, uses zinc dialkyl dithiophosphate (ZDDP) 0.5 weight part and 2,6-di-t-butyl alpha, alpha-dimethyl amido p-cresol 0.5 weight part to combine.
Isopropylcarbinol, 20 weight parts;
Organic solvent selects toluene and each 6.5 weight parts of ethyl acetate.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 20g additive by embodiment 1, obtained biofuel 7 is a yellow transparent liquid.
Embodiment 8
Prepare another kind of biofuel, design common diesel weight accounting 62% in biofuel, methanol-based fuel accounting 30%, measures 30.0g methyl alcohol, the conventional 0# diesel oil of 620g, 270g Witconol 2301, and binder component is changed into:
Emulsifying agent 25 weight part, wherein SP-80 emulsifying agent 20 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 25 weight part, comprises petroleum sodium sulfonate 10 weight part, barium mahogany sulfonate 15 weight part;
Tritolyl phosphate, 8 weight parts;
Isooctyl ester nitrate, 4 weight parts;
Help emulsifying dispersant, T165A product 0.2 weight part of use diethyl succinate 0.8 weight part, derivatives of poly (iso) butene series combines;
Oxidation inhibitor, uses zinc dialkyl dithiophosphate (ZDDP) 0.5 weight part.
Isopropylcarbinol, 18 weight parts;
Organic solvent selects toluene, 18.5 weight parts.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 80g additive by embodiment 1, obtained biofuel 8 is a yellow transparent liquid.
Embodiment 9
Prepare another kind of biofuel, design common diesel weight accounting 62% in biofuel, methanol-based fuel accounting 30%, measures 270.0g methyl alcohol, 30g methylcarbonate, the conventional 0# diesel oil of 620g, and binder component is changed into:
Emulsifying agent 15 weight part, wherein SP-80 emulsifying agent 10 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 20 weight part, comprises petroleum sodium sulfonate 15 weight part, barium mahogany sulfonate 5 weight part;
Tritolyl phosphate, 12 weight parts;
Isooctyl ester nitrate, 8 weight parts;
Help emulsifying dispersant, T165A product 1.5 weight part of use dimethyl succinate 1.5 weight part, derivatives of poly (iso) butene series combines;
Oxidation inhibitor, uses zinc dialkyl dithiophosphate (ZDDP) 1.0 weight part.
Isopropylcarbinol, 26 weight parts;
Organic solvent selects methylcarbonate, 15 weight parts.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 80g additive by embodiment 1, obtained biofuel 9 is a yellow transparent liquid.Owing to adding the methylcarbonate of low-flash and low melting point, obtained biofuel is higher compared with other biofuel flash-point, but condensation point and cold filter clogging temperature all greatly reduce, and it can replace common low temperature diesel oil for extremely frigid zones operation.
Embodiment 10
Prepare another kind of biofuel, design common diesel weight accounting 62% in biofuel, methanol-based fuel accounting 30%, measure 300.0g methyl alcohol and the conventional 0# diesel oil of 620g, binder component is changed into:
Emulsifying agent 15 weight part, wherein SP-80 emulsifying agent 10 weight part, OP-10 emulsifying agent 5 weight part;
PH value buffer reagent 20 weight part, comprises petroleum sodium sulfonate 10 weight part, barium mahogany sulfonate 10 weight part;
Tritolyl phosphate, 12 weight parts;
Isooctyl ester nitrate, 4 weight parts;
Help emulsifying dispersant, T165A product 0.5 weight part of use dimethyl succinate 1.5 weight part, derivatives of poly (iso) butene series combines;
Oxidation inhibitor, uses zinc dialkyl dithiophosphate (ZDDP) 2.0 weight part.
Isopropylcarbinol, 25 weight parts;
Organic solvent 20 weight part, selects toluene 10 weight part and diethyl carbonate (DMC) 10 weight part to combine.
After having prepared additive by the method for embodiment 1, get the method configuration biofuel of 80g additive by embodiment 1, obtained biofuel 10 is a yellow transparent liquid.
Embodiment 11
By embodiment 31 technology distortion in conjunction with the embodiments, in formula, the component of methyl alcohol, oleic acid, conventional 0# diesel oil is identical with embodiment 3 with content, the component of additive formulations is identical with embodiment 1 with content, preparation process is as different from Example 3: methyl alcohol adds the 2g vitriol oil after mixing with oleic acid, heat to 70 DEG C of cooling depicklings, dehydration, all the other preparation process are identical, obtain biofuel 11, and its integration test index is as shown in table 2.
The parameter of table 2 part biological diesel oil
| Biofuel 11 | Biofuel 12 | Biofuel 14 | |
| Density, kg/m 3 | 838.8 | 878 | 910 |
| Viscosity, mm 2/s | 3.520 | 4.3 | 95 |
| Flash-point, DEG C | 66.3 | 72 | 70 |
| Condensation point, DEG C | 0 | 0 | -6 |
| Cold filter clogging temperature, DEG C | 5 | 2 | 3 |
| Acidity, mgKOH/100mL | 0.86 | 0.51 | 0.42 |
| Copper corrosion | 1a | 1a | 1a |
| 10% steams excess carbon residue, % | 0.01 | 0.007 | 0.01 |
| Moisture, % | Vestige | Vestige | Vestige |
| Machine is mixed | Nothing | Nothing | Nothing |
| Sulphur content, ppm | 348 | 330 | 241 |
| Initial boiling point, DEG C | 95.0 | 95 | Do not test |
| 10% recovered temperature, DEG C | 262 | ||
| 50% recovered temperature, DEG C | 268.5 | 330- | Do not test |
| 90% recovered temperature, DEG C | 342.4 | 347 | Do not test |
| 95% recovered temperature, DEG C | 360.0 | 360 | Do not test |
| Cetane index | 46.5 | 51.2 | 48 |
The present embodiment cetane value reaches 46.5, and flash-point reaches 66.3 DEG C, and fire row is high-volume lower than 25% of common 0# diesel oil, and be a kind of desirable biofuel, alternative common diesel is applied to diesel engine arts.In addition, help poly-owing to adding acid in this process, can play the effect of emulsifying agent, therefore also can consider not add emulsifying agent from cost-effective angle when preparation, and it is suitable with the product performance adding emulsifying agent obtained not add the product that emulsifying agent obtains.
Embodiment 12
Prepare a kind of biofuel 12 of use for diesel engine, the component of additive, content and technological process and embodiment 1 are roughly the same, mix in obtained additive and Witconol 2301 by weight 4:96,7mgKOH/100mL is less than to acidity with petroleum sodium sulfonate or barium mahogany sulfonate fine setting, can obtain the biofuel 12 of high fuel value, biofuel 12 can mix to dissolve each other with arbitrary proportion with conventional 0# diesel oil and uses.The feature of the present embodiment does not add conventional petrochemical diesel oil, obtained biofuel 12, and combustion heat value is high, and cetane index can reach 47, and " diesel oil " is only name because burning behavior is similar.Similar with embodiment 11, also can not add emulsifying agent in the present embodiment, but the product performance obtained quite or a little less than during preparation add the product of emulsifying agent.
Embodiment 13
Prepare a kind of biofuel 13 of use for diesel engine, the component of additive, content and technological process and embodiment 4 are roughly the same, mix in obtained additive and Witconol 2301 by weight 8:92,7mgKOH/100mL is less than to acidity with petroleum sodium sulfonate or barium mahogany sulfonate fine setting, can obtain the biofuel 13 of high fuel value, biofuel 13 can mix to dissolve each other with arbitrary proportion with conventional 0# diesel oil and uses.The feature of the present embodiment is identical with embodiment 12, does not namely add conventional petrochemical diesel oil, obtained biofuel 13, and combustion heat value is high, and cetane index can reach 46.7, and " diesel oil " is only name because burning behavior is similar.
Embodiment 14
Biofuel 6 obtained by embodiment 4 is concocted conventional heavy oil (commercially available 180# heavy oil by 20% volume ratio, purchased from Sinopec), condensation point can be made greatly to reduce, sufficient combustion, smoke discharge amount especially PM2.5 index is that the order of magnitude reduces, for original 10%, reach the emission standard of China and European Union.
Finally it should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is modified or equivalent replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
1. a biofuel, is characterized in that, based on the biofuel of 100 weight parts, comprising:
Methanol-based fuel 27 ~ 96 weight part;
Common diesel 0 ~ 70 weight part;
Additive 2 ~ 8 weight part;
Described methanol-based fuel is the mixture of methyl alcohol and oleic acid, or the mixture of methyl alcohol and carbinol-modified complex body, or carbinol-modified complex body;
Described carbinol-modified complex body, at least comprise in following material one or more: the ester class of the ethers of methyl alcohol and alcohol condensation and methyl alcohol and sour condensation;
Described additive its there is following composition, based on the additive of 100 weight parts, comprising:
Emulsifying agent 15 ~ 25 weight part;
PH value buffer reagent 20 ~ 33 weight part;
Tritolyl phosphate 8 ~ 12 weight part;
Isooctyl ester nitrate 4 ~ 8 weight part;
Help emulsifying dispersant 0.7 ~ 3 weight part;
Oxidation inhibitor 0.35 ~ 2 weight part;
Isopropylcarbinol 18 ~ 30 weight part;
Organic solvent 13 ~ 20 weight part;
Described pH value buffer reagent is the composite mixture of petroleum sodium sulfonate and barium mahogany sulfonate, and wherein petroleum sodium sulfonate accounts for 10 ~ 25 weight parts, and barium mahogany sulfonate accounts for 5 ~ 15 weight parts, and the weight of composite mixture is not less than 20 weight parts, is no more than 33 weight parts;
Described organic solvent at least comprise in following solvent one or more: aromatic hydrocarbon solvent, ketones solvent, esters solvent, ether solvent;
Described emulsifying agent is the composite mixture of Span series emulsifying agent and twain series emulsifier, or the composite mixture of Span series emulsifying agent and OP-10 emulsifying agent, wherein Span series emulsifying agent accounts for 10 ~ 20 weight parts, TWEEN Series or OP-10 emulsifying agent account for 5 ~ 10 weight parts, and the weight of composite mixture is no more than 25 weight parts.
2. biofuel according to claim 1, is characterized in that: Span series emulsifying agent and twain series emulsifier, or the weight ratio of Span series emulsifying agent and OP-10 emulsifying agent is 2.5:1 ~ 4:1.
3. biofuel according to claim 1, it is characterized in that, described organic solvent at least comprise in following solvent one or more: toluene, methyl tertiary butyl ether, tert amyl methyl ether(TAME), methylcarbonate, and the mass ratio of isopropylcarbinol and organic solvent is 1:1 ~ 2:1.
4. biofuel according to claim 1, is characterized in that, described in help emulsifying dispersant, at least comprise one or more in following material: succinate, polyolefinic succinimide acid polyhydroxy alkyl ester and derivatives of poly (iso) butene.
5. biofuel according to claim 1, it is characterized in that, the oxidation inhibitor of described additive, at least comprise in following material one or more: amine type oxidation inhibitor, phenol type antioxidant, phenol amine type oxidation inhibitor, sulphur phosphorous antioxygen corrosion inhibitor, dialkyl dithiocarbamate, 124 Triazole compounds and thiadiazole compound.
6. biofuel according to claim 1, is characterized in that: when methanol-based fuel is the mixture of methyl alcohol and carbinol-modified complex body, or when being the mixture of methyl alcohol and oleic acid, methyl alcohol weight accounting is in the mixture 10 ~ 90%.
7. prepare a method for biofuel according to claim 1, it is characterized in that:
(1), after being dissolved completely in organic solvent by oxidation inhibitor, first kind component is fully mixed with into isooctyl ester nitrate;
(2) by two components in pH value buffer reagent, tritolyl phosphate with help emulsifying dispersant to mix, then be heated to stop after pH value buffer reagent dissolves completely in constantly stirring, be cooled to < 40 DEG C in Keep agitation after, isopropylcarbinol is added and stirs, be prepared into Equations of The Second Kind component;
(3) the 3rd class component is obtained after kind of the component of two in emulsifying agent being mixed;
(4) add the 3rd class component after first kind component being mixed with Equations of The Second Kind component to mix, obtain additive;
(5) additive being joined in methanol-based fuel, by adding petroleum sodium sulfonate or barium mahogany sulfonate makes its acidity be less than 7mg KOH/100mL, obtaining biofuel.
8. preparation method according to claim 7, it is characterized in that, described methanol-based fuel is the mixture of methyl alcohol and oleic acid, it is adopted and prepares with the following method: mixed with oleic acid by methyl alcohol, and add and account for the promoter of oleic acid weight than 0.5 ~ 3% and help mixed poly-, then removal promoter and dehydration obtain first kind component, and described promoter is the catalyzer of esterification, is selected from the one in following substances: homogeneous catalyst, solid catalyst, ionic-liquid catalyst, enzyme catalyst.
9. the preparation method according to claim 7 or 8, it is characterized in that: described stirring or blending means comprise the random shearing stirring of rotary agitator, periodicity or corner cut, magnetic swashs resonance mixing and the mixing of additional reaction pressure, and when use adds reaction pressure mixing, reaction pressure is no more than 25MPa.
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| CN105219449A (en) * | 2014-06-18 | 2016-01-06 | 雷菊花 | A kind of biomass low-carbon diesel oil |
| CN105273773A (en) * | 2014-06-18 | 2016-01-27 | 雷菊花 | Low-carbon biological methanol high-proportion substitute diesel oil and preparation method thereof |
| CN106190376A (en) * | 2016-08-23 | 2016-12-07 | 陈晓锋 | A kind of diesel oil emulsifier and its preparation method and application |
| CN107057785A (en) * | 2017-05-25 | 2017-08-18 | 滕晓明 | A kind of multi-functional fuel oil additive |
| CN114181745A (en) * | 2021-12-23 | 2022-03-15 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | Clean fuel and preparation method thereof |
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| CN1232072A (en) * | 1998-04-16 | 1999-10-20 | 北京百利威科技发展中心 | Cleaning agent for fuel system of automobile |
| CN101948702A (en) * | 2010-09-30 | 2011-01-19 | 昆明理工大学 | Alcohol-based biological fuel oil for boiler and preparation method thereof |
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| CN1232072A (en) * | 1998-04-16 | 1999-10-20 | 北京百利威科技发展中心 | Cleaning agent for fuel system of automobile |
| CN101948702A (en) * | 2010-09-30 | 2011-01-19 | 昆明理工大学 | Alcohol-based biological fuel oil for boiler and preparation method thereof |
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