CN114478654B - Preparation method of ferrocene-porphyrin metal complex, ferrocene-porphyrin metal complex and bimetallic fuel additive - Google Patents
Preparation method of ferrocene-porphyrin metal complex, ferrocene-porphyrin metal complex and bimetallic fuel additive Download PDFInfo
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- CN114478654B CN114478654B CN202111670855.1A CN202111670855A CN114478654B CN 114478654 B CN114478654 B CN 114478654B CN 202111670855 A CN202111670855 A CN 202111670855A CN 114478654 B CN114478654 B CN 114478654B
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- ferrocene
- porphyrin
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- 239000002816 fuel additive Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 49
- 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 claims abstract description 32
- -1 porphyrin metal complex Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 62
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 32
- 229910052697 platinum Inorganic materials 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 150000004032 porphyrins Chemical class 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 14
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Chemical class 0.000 claims description 13
- 239000002184 metal Chemical class 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 229920002367 Polyisobutene Polymers 0.000 claims description 11
- 239000000295 fuel oil Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 229960002317 succinimide Drugs 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims 1
- 239000003747 fuel oil additive Substances 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 72
- 238000011069 regeneration method Methods 0.000 abstract description 72
- 239000000446 fuel Substances 0.000 abstract description 42
- 239000002245 particle Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 12
- 238000012423 maintenance Methods 0.000 abstract description 7
- 239000002828 fuel tank Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000004939 coking Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- ZNZBLMAKBVIIIQ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Ce] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Ce] ZNZBLMAKBVIIIQ-UHFFFAOYSA-N 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 8
- 230000002035 prolonged effect Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- VFHDWGAEEDVVPD-UHFFFAOYSA-N chembl507897 Chemical compound C1=CC(O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(O)=CC=1)=C1C=CC(=N1)C(C=1C=CC(O)=CC=1)=C1C=CC(N1)=C1C=2C=CC(O)=CC=2)=C2N=C1C=C2 VFHDWGAEEDVVPD-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- JLSFGHJZDAFBQP-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin-2-amine Chemical compound NC1=C2NC(=C1)C(=C1C=CC(=N1)C(=C1C=CC(N1)=C(C=1C=CC(N=1)=C2C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 JLSFGHJZDAFBQP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- NPRDEIDCAUHOJU-UHFFFAOYSA-N [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NPRDEIDCAUHOJU-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GSVIBLVMWGSPRZ-UHFFFAOYSA-N cerium iron Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Ce].[Ce] GSVIBLVMWGSPRZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
-
- 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
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention discloses a preparation method of a ferrocene-porphyrin metal complex, the ferrocene-porphyrin metal complex and a bimetallic fuel additive. The preparation method of the ferrocene-porphyrin metal complex comprises the following steps: dissolving porphyrin metal complex and ferrocene with carboxyl or aldehyde group in a solvent B, adding tertiary amine for reaction, and removing the solvent to obtain the ferrocene-porphyrin metal complex. The bimetallic fuel additive can be conveniently added into a fuel tank during refueling, can be uniformly mixed with fuel, reduces the formation of particles in an engine, can effectively solve the problem that a diesel engine particle catcher (DPF) fails to passively regenerate after tail gas reaches the DPF, and reduces the number of active regeneration times, thereby achieving the effects of maintaining the DPF particle catcher, saving fuel and reducing maintenance times and cost.
Description
Technical Field
The invention belongs to the technical field of fuel additives, and particularly relates to a preparation method of a ferrocene-porphyrin metal complex, the ferrocene-porphyrin metal complex and a bimetallic fuel additive.
Background
The discharge standard of national VI is implemented in China nationwide in 2021, 7 and 1, and the discharge of particulate matters is greatly improved. The prior technical route of improving the combustion temperature in a cylinder and adding an SCR system used in the five-emission stage of China can not meet the requirements of the emission standard of particulate matters, and a particle catcher DPF is required to be additionally arranged to meet the emission requirements. With the implementation of the increasingly stringent exhaust emission regulations in europe, america, the day, china, etc., the demand for diesel particulate traps DPF as an effective means for reducing the emission of particulate matters will rapidly increase.
The DPF is a honeycomb ceramic sintered structure, and a noble metal catalyst is coated on the DPF. When particulate matter reaches the DPF, it is intercepted by the pore canal and accumulated to a certain extent, the accumulated particulate matter needs to be burned off, which is called regeneration. There are two methods of DPF regeneration, one is passive regeneration and one is active regeneration. Passive regeneration is performed during running, and the catalyst coating on the DPF is utilized to burn off the particulate matters on the DPF at about 500 ℃, so that the DPF is kept smooth. Passive regeneration often fails due to vehicle traffic congestion, poor fuel quality, component failure, or exhaust temperatures in short-haul transport that do not reach the regeneration temperature. Frequent passive regeneration failure of the DPF can cause excessive accumulation of particulate matters on the DPF, increase of back pressure, increase of fuel consumption and engine failure, and active regeneration is needed. The active regeneration usually adopts in-situ parking, and fuel is injected into the aftertreatment system for 40 minutes to 1 hour when the engine runs at idle speed, so that the temperature of the tail gas is increased to 500-600 ℃ and the particulate matters are burnt. The active regeneration consumes oil and is time-consuming, so that extra cost is added for the vehicle owner, and meanwhile, if the active regeneration system is wrong or fails to control, too much oil is injected, the local temperature is too high, and the DPF can be burnt and scrapped, so that larger economic loss is caused. So that the smooth progress of passive regeneration is the necessary requirement of the national VI to discharge the diesel vehicle to reach the standard.
At present, when the DPF blockage reaches a certain threshold value, active regeneration cannot be completed, and only offline regeneration can be performed. Off-line regeneration is to remove the DPF from the vehicle, reversely purge the DPF by using high-pressure air or a particle trapping liquid in a special regeneration device, clean the particles, dry the DPF by using hot air, and then load the DPF back to the vehicle after detection. Chinese patent CN112943413a discloses a device and method for detecting DPF regeneration of diesel vehicle; chinese patent CN111720190a discloses a particulate matter trapping liquid for a diesel vehicle DPF regeneration device and a preparation method thereof. This technique of cleaning the DPF requires maintenance of the vehicle, is time consuming and laborious, and is prone to degrading the DPF filtration efficiency by wall flow type micro Kong Dachuan in the DPF. Chinese patent CN104845682a discloses a fuel catalyst for an internal combustion engine of an automobile, which is composed of tourmaline, alumina, iron oxide and ceria, and the catalyst is put into the oil inlet end of a fuel filter to play the roles of saving oil and removing carbon deposit, but the alumina, the iron oxide, the ceria and the like are all particles with about 250 μm, and can not be dissolved in the fuel and have no mention of the application in regeneration of a DPF particle catcher. Chinese patent CN102125845a discloses a nano quantum dot grade diesel vehicle fuel additive catalyst and its preparation method and application, wherein trivalent cerium metal salt or a mixture of trivalent cerium and trivalent iron metal salt is added into alcohol ether, and a two-stage heating method is adopted to prepare cerium oxide catalyst or cerium-iron composite oxide. Although the particle size of the catalyst is below 5nm, the catalyst is still insoluble in fuel oil and the nano particles are easy to agglomerate, so that the use of the catalyst is affected.
Therefore, it is now necessary to develop a diesel additive which can be conveniently added into a fuel tank during refueling and can be uniformly mixed with fuel, so that the formation of particulate matters in the interior of an engine can be reduced, the regeneration mileage of a DPF can be remarkably improved after the exhaust reaches the DPF, the regeneration time of the DPF can be shortened, the active regeneration times can be reduced, the fuel can be saved, and the maintenance times and the cost of the DPF of a vehicle can be reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a ferrocene-porphyrin metal complex, the ferrocene-porphyrin metal complex and a bimetallic fuel additive. The bimetallic fuel additive is conveniently added into the fuel tank during refueling, can be uniformly mixed with fuel, reduces the formation of particles in the engine, can effectively solve the problem that the passive regeneration of a diesel engine particle catcher (DPF) fails after tail gas reaches the DPF, and reduces the number of active regeneration times, thereby achieving the effects of maintaining the DPF particle catcher, saving fuel and reducing maintenance times and cost.
The invention aims at providing a preparation method of a ferrocene-porphyrin metal complex.
The method comprises the following steps:
(1) Porphyrin and metal salt with active hydroxyl or amino are dissolved in a solvent A, and the reaction is carried out under stirring;
(2) Cooling the mixture after the reaction in the step (1) to room temperature, pouring the mixture into ice water to generate precipitate, and carrying out suction filtration, washing and drying to obtain porphyrin metal complex;
(3) Dissolving porphyrin metal complex and ferrocene with carboxyl or aldehyde group in a solvent B, adding tertiary amine for reaction, and removing the solvent to obtain the ferrocene-porphyrin metal complex.
In a preferred embodiment of the present invention,
in the step (1), the step of (a),
the structure of the porphyrin with active hydroxyl or amino is as follows:
R 1 、R 2 、R 3 identical or different and independently selected from H, OH, NH 2 、Cl、Br、NO 2 、C n H 2n+1 Or OC (alpha) n H 2n+1 Wherein n=1 to 20; and/or the number of the groups of groups,
the metal salt is at least one of chloride, nitrate, acetate and perchlorate of cerium, platinum, ruthenium and palladium, preferably chloride, nitrate, acetate and perchlorate of cerium and platinum; and/or the number of the groups of groups,
the solvent A is at least one of pyridine, N 'N-dimethylformamide, N' N-dimethylacetamide, acetonitrile and benzonitrile;
the molar ratio of the porphyrin with active hydroxyl or amino to the metal salt is 1:0.1-1:10;
the concentration of the porphyrin with active hydroxyl or amino after being dissolved in the solvent A is 0.01-10 mol/L;
the concentration of the metal salt after being dissolved in the solvent A is 0.01-10 mol/L;
the reaction temperature is 50-160 ℃, preferably 120-150 ℃, and the reaction time is 1-48 h, preferably 1-10 h.
In a preferred embodiment of the present invention,
in the step (3), the step of (c),
the ferrocene with carboxyl or aldehyde group is one or more of ferrocene monocarboxylic acid, ferrocene dicarboxylic acid, ferrocene monoformaldehyde and ferrocene dicarboxaldehyde; and/or the number of the groups of groups,
the solvent B is at least one of dichloromethane, dichloroethane and chloroform; and/or the number of the groups of groups,
the tertiary amine is at least one of trimethylamine, triethylamine and pyridine;
the molar ratio of the porphyrin metal complex to the ferrocene with carboxyl or aldehyde groups is in the range of 1:0.02-1:10, preferably 1:0.05-1:2, and more preferably 1:0.5-1:2;
the concentration of the porphyrin metal complex after being dissolved in the solvent B is 0.01-10 mol/L;
the concentration of the ferrocene with carboxyl or aldehyde group after being dissolved in the solvent B is 0.01-10 mol/L;
the volume ratio of the tertiary amine to the solvent B is 1-10: 100;
the reaction temperature is preferably 0-60 ℃ under reflux condition, and the reaction time is 0.5-20 h, preferably 5-20 h.
It is a second object of the present invention to provide a ferrocene-porphyrin metal complex prepared by the method of one of the objects of the present invention.
It is a further object of the present invention to provide a bimetallic fuel additive comprising the ferrocene-porphyrin metal complex of the second object of the present invention.
The fuel additive is prepared from components including solvent oil, an amine detergent and the ferrocene-porphyrin metal complex;
the components are calculated according to the weight portions,
100 parts by weight of solvent oil;
0.1 to 30 parts by weight of an amine detergent; preferably 10 to 20 parts by weight; more preferably 10 to 15 parts by weight;
0.01 to 15 parts by weight of ferrocene-porphyrin metal complex; preferably 1 to 5 parts by weight.
In a preferred embodiment of the present invention,
an antioxidant can be added into the fuel additive.
In a preferred embodiment of the present invention,
calculated by 100 weight parts of solvent oil,
0.1 to 1.5 parts by weight of antioxidant; preferably 0.5 to 1 part by weight.
In a preferred embodiment of the present invention,
the solvent oil is at least one of alkane solvent oil and aromatic hydrocarbon solvent oil, and is used for dissolving all components in the additive; and/or the number of the groups of groups,
the amine detergent is at least one of polyisobutylene succinimide, polyisobutylene amine and polyether amine, and is used for removing carbon deposition in an engine, so that the carbon deposition is discharged along with waste gas and is trapped by a particle trap; and/or the number of the groups of groups,
the antioxidant may be a conventional antioxidant in the art, and in the present invention, phenylenediamine, alkylphenylenediamine, p-tert-butylphenol or 2, 6-di-tert-butyl-p-cresol (BHT) may be preferable.
The fuel additive of the invention can be added with conventional components in the field, such as polyether, and the dosage is also conventional, and the technical personnel can adjust according to actual conditions.
The fourth object of the present invention is to provide a method for preparing the bimetallic fuel additive of the third object of the present invention.
The method comprises the following steps:
and uniformly mixing the components according to the dosage to obtain the bimetallic fuel additive.
The fifth object of the invention is to provide a fuel additive of the third object of the invention or the use of the fuel additive prepared by the method of the fourth object of the invention in regeneration of a particle catcher of a diesel vehicle.
The fuel additive is used by blending with fuel oil according to the proportion of 1/1000-1/20.
The invention adopts the following specific technical scheme:
the preparation method of the ferrocene-porphyrin metal complex preferably comprises the following steps: firstly, porphyrin and metal salt with active hydroxyl or amino are dissolved in a solvent A, wherein the concentration of the porphyrin is 0.01-10 mol/L, and the concentration of the metal salt is 0.01-10 mol/L, and the metal salt comprises chloride, nitrate, acetate or perchlorate of cerium, platinum, ruthenium or palladium; secondly, heating the reaction system to 50-160 ℃ and reacting for 1-48 h under magnetic stirring; thirdly, cooling the reaction mixture to room temperature, pouring the reaction mixture into ice water to generate precipitate, and obtaining porphyrin metal complex through suction filtration, washing and drying; fourthly, dissolving the porphyrin metal complex obtained in the third step and ferrocene with carboxyl or aldehyde group in a solvent B, adding tertiary amine, and reacting for 0.5 to 20 hours at the temperature of 0 to 60 ℃, wherein the concentration of the porphyrin metal complex is 0.01 to 10mol/L, and the concentration of the ferrocene with carboxyl or aldehyde group is 0.01 to 10mol/L; and fifthly, evaporating the solvent from the reaction mixture in the fourth step to obtain the ferrocene-porphyrin metal complex.
The preparation method of the bimetallic fuel additive preferably comprises the steps of uniformly mixing 0.01-15 parts by weight of ferrocene-porphyrin metal complex, 0.1-30 parts by weight of amine detergent, 100 parts by weight of solvent oil and 0.1-1.5 parts by weight of antioxidant at 20-60 ℃ to prepare the bimetallic fuel additive.
The beneficial effects of the invention are as follows:
under normal working conditions, the exhaust temperature of the conventional diesel vehicle is 200-400 ℃, the ignition point of particles is often up to 450 ℃, and the passive regeneration of the catcher is difficult to realize; after the DPF regeneration additive is added into the fuel, the fuel and the catalyst are mixed and combusted, and the formed PM has the metal catalyst closely adhered, so that the PM combustion temperature (namely, the temperature at which PM accumulation and regeneration on the DPF reach balance) is reduced.
The bimetallic fuel additive is used by blending the additive and fuel oil according to the proportion of 1/1000-1/20, has good solubility, can effectively solve the problem of passive regeneration failure of a DPF particle catcher of a diesel engine, and reduces the number of active regeneration times, thereby achieving the effects of maintaining the DPF particle catcher, saving oil and reducing maintenance times and cost.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The starting materials used in the examples were all conventional commercially available.
Equilibrium point temperature test reference standard: technical requirements of the exhaust aftertreatment device of the T/CAEPI 12.3-2017 diesel vehicle part 3: diesel Particulate Filter (DPF).
Example 1
Preparation of porphyrin metal complex (cerium porphyrin): 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50 mmol) and cerium acetate (150 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 150 ℃ to react for 8h under magnetic stirring, the reaction mixture is poured into ice water, cerium porphyrin is separated out, suction filtration is carried out, deionized water is used for washing, and vacuum drying is carried out, so that porphyrin-cerium complex with active hydroxyl is obtained.
Preparation of ferrocene-porphyrin cerium complex: and (3) dissolving 20mmol of the porphyrin cerium metal complex with the active hydroxyl and 15mmol of ferrocene dicarboxylic acid in 50mL of dichloromethane, adding 1mL of triethylamine, reacting for 6h under a reflux condition, and evaporating the solvent after the reaction is finished to obtain the ferrocene-porphyrin metal complex.
Preparation of fuel additive containing ferrocene-porphyrin cerium complex: 1.1 parts by weight of ferrocene-cerium porphyrin complex, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of 6# solvent oil and 0.6 parts by weight of p-phenylenediamine are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene-cerium porphyrin complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-cerium porphyrin complex bimetal is mixed with fuel according to the volume ratio of 1:10, the fuel additive is well dispersed, and the fuel additive is placed for 12 months without layering and precipitation.
Properties of fuel additive containing ferrocene-porphyrin cerium complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:800, and after the fuel additive is added, the temperature of the balance point is reduced to 316 ℃ and is reduced by 84 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of the air-fuel loss of the 1-4 cylinder needle valve lift of 0.1mm after the fuel additive containing the ferrocene-porphyrin cerium complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000 is 26.3%, which shows that the fuel additive containing the ferrocene-porphyrin cerium complex has excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing ferrocene-cerium porphyrin complex is added into diesel oil, and the addition concentration is 10mg/kg (based on the total content of iron and cerium). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing ferrocene-cerium porphyrin complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels about 5000 km.
Example 2
Preparation of porphyrin metal complex (platinum porphyrin): monoamino tetraphenyl porphyrin (400 mmol) and platinum chloride (200 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 120 ℃ to react for 2h under magnetic stirring, the reaction mixture is poured into ice water, the product is separated out, filtered, washed with deionized water and dried in vacuum, and the monoamino tetraphenyl porphyrin-platinum complex is obtained.
Preparation of ferrocene-porphyrin platinum complex: 200mmol of monoamino tetraphenyl porphyrin-platinum metal complex and 400mmol of ferrocene dicarboxylic acid are taken and dissolved in 50mL of dichloroethane, 2mL of triethylamine is added, the reaction is carried out for 16h under the reflux condition, and the solvent is distilled off after the reaction is finished, so that the ferrocene-porphyrin platinum complex is obtained.
Preparation of a bimetallic fuel additive containing ferrocene-porphyrin platinum complex: 2.3 parts by weight of ferrocene-porphyrin platinum complex, 14 parts by weight of polyisobutene amine, 100 parts by weight of 120# solvent oil and 0.6 part by weight of antioxidant BHT are uniformly mixed at 50 ℃ to prepare the bimetallic fuel additive containing the ferrocene-porphyrin platinum complex.
Solubility of fuel additive containing ferrocene-porphyrin platinum complex bimetal: after the fuel additive containing ferrocene-porphyrin platinum complex bimetal is mixed with fuel according to the volume ratio of 1:10, the fuel additive is well dispersed, and the fuel additive is placed for 12 months without layering and precipitation.
Performance of fuel additive containing ferrocene-porphyrin platinum complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the ferrocene-porphyrin platinum complex is added into diesel oil according to the volume ratio of 1:100, and after the fuel additive is added, the temperature of the balance point is reduced to 309 ℃ and is reduced by 91 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of air-fuel loss is 23.5% after the fuel additive containing the ferrocene-porphyrin platinum complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000, and the fuel additive containing the ferrocene-porphyrin platinum complex has excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing ferrocene-porphyrin platinum complex is added into diesel oil, and the addition concentration is 10mg/kg (based on the total content of iron and cerium). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing ferrocene-porphyrin platinum complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels about 5500 km.
Example 3
Preparation of porphyrin metal complex (cerium porphyrin): 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50 mmol) and cerium acetate (150 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 150 ℃ to react for 8h under magnetic stirring, the reaction mixture is poured into ice water, cerium porphyrin is separated out, suction filtration is carried out, deionized water is used for washing, and vacuum drying is carried out, so that porphyrin-cerium complex with active hydroxyl is obtained.
Preparation of ferrocene-porphyrin cerium complex: and (3) dissolving 20mmol of the porphyrin cerium metal complex with the active hydroxyl and 15mmol of ferrocene dicarboxylic acid in 50mL of dichloromethane, adding 1mL of triethylamine, reacting for 6h under a reflux condition, and evaporating the solvent after the reaction is finished to obtain the ferrocene-porphyrin metal complex.
Preparation of fuel additive containing ferrocene-porphyrin cerium complex: 5.0 parts by weight of ferrocene-cerium porphyrin complex, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of 6# solvent oil and 0.6 parts by weight of p-phenylenediamine are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene-cerium porphyrin complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-cerium porphyrin complex bimetal is mixed with fuel according to the volume ratio of 1:10, the fuel additive is well dispersed, and the fuel additive is placed for 12 months without layering and precipitation.
Properties of fuel additive containing ferrocene-porphyrin cerium complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:300, and after the fuel additive is added, the temperature of the balance point is reduced to 306 ℃ and is reduced by 94 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of air-fuel loss is 23.0% when the fuel additive containing the ferrocene-porphyrin cerium complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000, and the fuel additive containing the ferrocene-porphyrin cerium complex has excellent effect of removing carbon deposition of an engine after the fuel additive is lifted by a needle valve lift of 0.1mm of a 1-4 cylinder.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing ferrocene-cerium porphyrin complex is added into diesel oil, and the addition concentration is 10mg/kg (based on the total content of iron and cerium). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing ferrocene-cerium porphyrin complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels about 5500 km.
Example 4
Preparation of porphyrin metal complex (cerium porphyrin): 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50 mmol) and cerium acetate (150 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 150 ℃ to react for 8h under magnetic stirring, the reaction mixture is poured into ice water, cerium porphyrin is separated out, suction filtration is carried out, deionized water is used for washing, and vacuum drying is carried out, so that porphyrin-cerium complex with active hydroxyl is obtained.
Preparation of ferrocene-porphyrin cerium complex: and (3) dissolving 20mmol of the porphyrin cerium metal complex with the active hydroxyl and 15mmol of ferrocene dicarboxylic acid in 50mL of dichloromethane, adding 1mL of triethylamine, reacting for 6h under a reflux condition, and evaporating the solvent after the reaction is finished to obtain the ferrocene-porphyrin metal complex.
Preparation of fuel additive containing ferrocene-porphyrin cerium complex: 3.5 parts by weight of ferrocene-cerium porphyrin complex, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of 6# solvent oil and 0.6 part by weight of p-phenylenediamine are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene-cerium porphyrin complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-cerium porphyrin complex bimetal is mixed with fuel according to the volume ratio of 1:10, the fuel additive is well dispersed, and the fuel additive is placed for 12 months without layering and precipitation.
Properties of fuel additive containing ferrocene-porphyrin cerium complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:500, and after the fuel additive is added, the temperature of the balance point is reduced to 314 ℃ and is reduced by 86 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of the gas-time loss of the 1-4 cylinder needle valve lift of 0.1mm after the fuel additive containing the ferrocene-porphyrin cerium complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 25.4%, which shows that the fuel additive containing the ferrocene-porphyrin cerium complex has excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing ferrocene-cerium porphyrin complex is added into diesel oil, and the addition concentration is 10mg/kg (based on the total content of iron and cerium). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing ferrocene-cerium porphyrin complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels about 5000 km.
Example 5
Preparation of porphyrin metal complex (platinum porphyrin): monoamino tetraphenyl porphyrin (400 mmol) and platinum chloride (200 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 120 ℃ to react for 2h under magnetic stirring, the reaction mixture is poured into ice water, the product is separated out, filtered, washed with deionized water and dried in vacuum, and the monoamino tetraphenyl porphyrin-platinum complex is obtained.
Preparation of ferrocene-porphyrin platinum complex: 200mmol of monoamino tetraphenyl porphyrin-platinum metal complex and 400mmol of ferrocene dicarboxylic acid are taken and dissolved in 50mL of dichloroethane, 2mL of triethylamine is added, the reaction is carried out for 16h under the reflux condition, and the solvent is distilled off after the reaction is finished, so that the ferrocene-porphyrin platinum complex is obtained.
Preparation of a bimetallic fuel additive containing ferrocene-porphyrin platinum complex: 5.0 parts by weight of ferrocene-porphyrin platinum complex, 14 parts by weight of polyisobutene amine, 100 parts by weight of 120# solvent oil and 0.6 part by weight of antioxidant BHT are uniformly mixed at 50 ℃ to prepare the bimetallic fuel additive containing the ferrocene-porphyrin platinum complex.
Solubility of fuel additive containing ferrocene-porphyrin platinum complex bimetal: after the fuel additive containing ferrocene-porphyrin platinum complex bimetal is mixed with fuel according to the volume ratio of 1:10, the fuel additive is well dispersed, and the fuel additive is placed for 12 months without layering and precipitation.
Performance of fuel additive containing ferrocene-porphyrin platinum complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the ferrocene-porphyrin platinum complex is added into diesel according to the volume ratio of 1:500, and after the fuel additive is added, the temperature of the balance point is reduced to 302 ℃ and is reduced by 98 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of air-fuel loss is 21.3% when the fuel additive containing the ferrocene-porphyrin platinum complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000, and the fuel additive containing the ferrocene-porphyrin platinum complex has excellent effect of removing carbon deposition of an engine after the fuel additive is lifted by a needle valve lift of 0.1mm of a 1-4 cylinder.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing ferrocene-porphyrin platinum complex is added into diesel oil, and the addition concentration is 10mg/kg (based on the total content of iron and platinum). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing ferrocene-porphyrin platinum complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels about 5500 km.
Comparative example 1
Preparation of porphyrin metal complex (cerium porphyrin): 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50 mmol) and cerium acetate (150 mmol) are dissolved in N' N-dimethylformamide (50 mL), the reaction system is heated to 150 ℃ to react for 8h under magnetic stirring, the reaction mixture is poured into ice water, cerium porphyrin is separated out, suction filtration is carried out, deionized water is used for washing, and vacuum drying is carried out, so that porphyrin-cerium complex with active hydroxyl is obtained.
Preparation of a fuel additive containing porphyrin cerium complex: 1.1 parts by weight of porphyrin cerium complex, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of 6# solvent oil and 0.6 part by weight of p-phenylenediamine are uniformly mixed at 30 ℃ to prepare the fuel additive containing the porphyrin cerium complex.
Performance of fuel additive containing porphyrin cerium complex: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the temperature of the balance point is 400 ℃ before the fuel additive is added, the fuel additive containing the porphyrin cerium complex is added into diesel according to the volume ratio of 1:800, and after the fuel additive is added, the temperature of the balance point is reduced to 345 ℃ and is reduced by 55 ℃.
Referring to the method and technical requirements specified in SH/T0764-2005 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve of a 1-4 cylinder of fuel without adding fuel additive is 0.1 mm; the average value of the gas-fuel loss of the 1-4 cylinder needle valve lift of 0.1mm after the fuel additive containing the porphyrin cerium complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 29.7%, which shows that the fuel additive containing cerium porphyrin has a certain effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, a fuel additive containing porphyrin cerium complex is added into diesel oil, and the addition concentration is 10mg/kg (calculated by cerium content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and DPF triggers regeneration after the fuel additive containing cerium porphyrin is added, so that DPF regeneration interval mileage is prolonged after the vehicle actually travels about 3000 km.
Comparative example 2
Preparation of ferrocene-containing fuel additive: 1.1 parts by weight of ferrocene, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of 6# solvent oil and 0.6 part by weight of p-phenylenediamine are uniformly mixed at 30 ℃ to prepare the fuel additive containing ferrocene.
Properties of ferrocene-containing fuel additives: bench test is carried out by adopting a diesel WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, a post-treatment device system comprising a DOC, a particle catcher (DPF) and an SCR and a data acquisition system. The exhaust temperature is adjusted by adjusting the engine operating point, and the DPF sediment balance point temperature is measured, wherein the measurement starts from 300 ℃ and ends from 20 ℃ to 440 ℃ when the temperature is increased. The continuous passive regeneration equilibrium point temperature is determined by measuring the differential pressure change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), the equilibrium point temperature is 400 ℃ before the fuel additive is added, the ferrocene-containing fuel additive is added into diesel according to the volume ratio of 1:800, and after the fuel additive is added, the equilibrium point temperature is reduced to 353 ℃ and is reduced by 47 ℃.
Referring to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), nozzle coking detection is carried out, and the average value of air-fuel loss is 85.5% when the lift of a needle valve lift of a fuel 1-4 cylinder without adding a fuel additive; the average value of air-fuel loss of 0.1mm of needle valve lift of 1-4 cylinders after the ferrocene-containing fuel additive is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 30.3 percent, and the effect of removing carbon deposition of an engine is achieved to a certain extent.
A small truck carrying a 2.0LCTI diesel engine is adopted for a real vehicle test, the DPF volume of the vehicle is 3.3L, the maximum carbon loading is calibrated to be 20g, and the running mileage of the whole vehicle at a regeneration interval is about 500km. In the test process, the fuel additive containing ferrocene is added into diesel oil, and the addition concentration is 10mg/kg (calculated by iron content). Before the test, the DPF will trigger regeneration after the vehicle is expected to travel about 400 km, and DPF regeneration interval mileage is slightly prolonged after DPF trigger regeneration is about 1500 km in actual driving after fuel additive containing ferrocene is added.
It can be seen from examples 1 to 5 that: on one hand, compared with the fuel additive only containing porphyrin metal complex or ferrocene, the fuel additive disclosed by the invention can effectively reduce the temperature of the balance point, so that the passive regeneration failure of a DPF particle catcher of a diesel engine can be effectively solved, the active regeneration times are reduced, the regeneration mileage is prolonged, and the effects of maintaining the DPF particle catcher, saving oil and reducing the maintenance times and cost are achieved; on the other hand, the fuel additive can be conveniently added into a fuel tank during refueling, can be uniformly mixed with fuel, and can be kept stable for a long time after being mixed.
As can be seen from comparative examples 1-2 and example 1: the fuel additive of the embodiment 1 contains ferrocene-porphyrin cerium complex, so that compared with the additive only containing ferrocene or porphyrin metal complex, the fuel additive can effectively reduce the temperature of the balance point, thereby effectively solving the problem that the DPF particle catcher of the diesel engine fails to passively regenerate, reducing the active regeneration times and prolonging the regeneration mileage, and further achieving the effects of maintaining the DPF particle catcher, saving fuel and reducing the maintenance times and cost.
Claims (8)
1. A bimetallic fuel oil additive containing ferrocene-porphyrin metal complex is characterized in that:
the fuel additive is prepared from components including solvent oil, an amine detergent and the ferrocene-porphyrin metal complex;
the components are calculated according to the weight portions,
100 parts by weight of solvent oil;
0.1 to 30 parts by weight of an amine detergent;
0.01 to 15 parts by weight of ferrocene-porphyrin metal complex;
the preparation method of the ferrocene-porphyrin metal complex comprises the following steps:
(1) Porphyrin and metal salt with active hydroxyl or amino are dissolved in a solvent A, and the reaction is carried out under stirring;
(2) Cooling the mixture after the reaction in the step (1) to room temperature, pouring the mixture into ice water to generate precipitate, and carrying out suction filtration, washing and drying to obtain porphyrin metal complex;
(3) Dissolving porphyrin metal complex and ferrocene with carboxyl or aldehyde group in a solvent B, adding tertiary amine to react, and removing the solvent to obtain the ferrocene-porphyrin metal complex;
in the step (1), the step of (a),
the structure of the porphyrin with active hydroxyl or amino is as follows:
R 1 、R 2 、R 3 identical or different and independently selected from H, OH, NH 2 、Cl、Br、NO 2 、C n H 2n+1 Or OC (alpha) n H 2n+1 Wherein n=1 to 20;
the metal salt is at least one of chloride, nitrate, acetate and perchlorate of cerium and platinum.
2. The fuel additive of claim 1, wherein:
in the step (1), the step of (a),
the solvent A is at least one of pyridine, N 'N-dimethylformamide, N' N-dimethylacetamide, acetonitrile and benzonitrile;
the molar ratio of the porphyrin with active hydroxyl or amino to the metal salt is 1:0.1-1:10;
the concentration of the porphyrin with active hydroxyl or amino after being dissolved in the solvent A is 0.01-10 mol/L;
the concentration of the metal salt after being dissolved in the solvent A is 0.01-10 mol/L;
the reaction temperature is 50-160 ℃, and the reaction time is 1-48 h.
3. The fuel additive of claim 1, wherein:
in the step (3), the step of (c),
the ferrocene with carboxyl or aldehyde group is one or more of ferrocene monocarboxylic acid, ferrocene dicarboxylic acid, ferrocene monoformaldehyde and ferrocene dicarboxaldehyde; and/or the number of the groups of groups,
the solvent B is at least one of dichloromethane, dichloroethane and chloroform; and/or the number of the groups of groups,
the tertiary amine is at least one of trimethylamine, triethylamine and pyridine;
the molar ratio of the porphyrin metal complex to the ferrocene with carboxyl or aldehyde group is 1:0.02-1:10;
the concentration of the porphyrin metal complex after being dissolved in the solvent B is 0.01-10 mol/L;
the concentration of the ferrocene with carboxyl or aldehyde group after being dissolved in the solvent B is 0.01-10 mol/L;
the volume ratio of the tertiary amine to the solvent B is 1-10: 100;
the reaction time is 0.5-20 h.
4. The fuel additive of claim 1, wherein:
100 parts by weight of solvent oil;
10-20 parts by weight of an amine detergent;
1 to 5 parts by weight of ferrocene-porphyrin metal complex.
5. The fuel additive of claim 1, wherein:
an antioxidant can be added into the fuel additive.
6. The fuel additive of claim 1, wherein:
the solvent oil is at least one of alkane solvent oil and aromatic solvent oil; and/or the number of the groups of groups,
the amine detergent is at least one of polyisobutylene succinimide, polyisobutylene amine and polyether amine.
7. A method for preparing the fuel additive according to any one of claims 1 to 6, comprising:
and uniformly mixing the components according to the dosage to obtain the bimetallic fuel additive.
8. Use of a fuel additive according to any one of claims 1 to 6 or prepared by the method of claim 7 for regenerating a diesel particulate trap, characterized in that:
the fuel additive is used by blending with fuel oil according to the proportion of 1/1000-1/20.
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