CN114478654A - Preparation method of ferrocene-porphyrin metal complex, ferrocene-porphyrin metal complex and fuel additive containing bimetal - Google Patents
Preparation method of ferrocene-porphyrin metal complex, ferrocene-porphyrin metal complex and fuel additive containing bimetal Download PDFInfo
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- CN114478654A CN114478654A CN202111670855.1A CN202111670855A CN114478654A CN 114478654 A CN114478654 A CN 114478654A CN 202111670855 A CN202111670855 A CN 202111670855A CN 114478654 A CN114478654 A CN 114478654A
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- Prior art keywords
- ferrocene
- porphyrin
- metal complex
- solvent
- fuel additive
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Links
- 239000002816 fuel additive Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000008929 regeneration Effects 0.000 claims abstract description 75
- 238000011069 regeneration method Methods 0.000 claims abstract description 75
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 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 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003921 oil Substances 0.000 claims abstract description 30
- -1 porphyrin metal complex Chemical class 0.000 claims abstract description 28
- 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
- 239000003747 fuel oil additive Substances 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 63
- 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 56
- 238000000034 method Methods 0.000 claims description 33
- 229910052697 platinum Inorganic materials 0.000 claims description 31
- 239000000446 fuel Substances 0.000 claims description 27
- 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 18
- 125000002887 hydroxy group Chemical class [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
- 238000005406 washing Methods 0.000 claims description 10
- 125000003368 amide group Chemical class 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 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
- 239000000203 mixture Substances 0.000 claims description 8
- 229960002317 succinimide Drugs 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000012423 maintenance Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000004939 coking Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 10
- 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 9
- 230000008021 deposition Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002283 diesel fuel Substances 0.000 description 7
- 206010021198 ichthyosis Diseases 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 230000002035 prolonged effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000001291 vacuum drying 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
- 239000006185 dispersion Substances 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
- 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
- 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
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture 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
- 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
- 150000001242 acetic acid derivatives Chemical class 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
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002823 nitrates Chemical class 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
- 239000002994 raw material Substances 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
- 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
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 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
- 239000002699 waste material 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
Abstract
The invention discloses a preparation method of a ferrocene-porphyrin metal complex, the ferrocene-porphyrin metal complex and a fuel additive containing bimetal. The preparation method of the ferrocene-porphyrin metal complex comprises the following steps: dissolving the 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 fuel oil additive containing bimetal can be conveniently added into an oil tank when oil is added, and can be uniformly mixed with fuel oil, the formation of particulate matters is reduced in an engine, after tail gas reaches DPF, the problem that a diesel engine particle trap (DPF) fails in passive regeneration can be effectively solved, the active regeneration frequency is reduced, and therefore the effects of maintaining the DPF particle trap, saving oil and reducing the maintenance frequency and cost are achieved.
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 fuel additive containing bimetal.
Background
In 2021, 7 and 1, national VI emission standards are implemented nationwide, and the emission of particulate matters in the national VI emission standards is greatly tightened. The technical route of adding an SCR system for increasing the combustion temperature in a cylinder used in the fifth national emission stage cannot meet the requirement of particulate matter emission standard, and a particulate filter (DPF) must be added to meet the emission requirement. With the implementation of increasingly strict exhaust emission regulations in europe, the united states, the day, china, etc., the demand for a diesel particulate filter DPF as an effective device for reducing particulate emissions is rapidly increasing.
The DPF is a honeycomb ceramic sintered structure, and a noble metal catalyst is coated on the DPF. When the particulate matter reaches the DPF and is intercepted by the pore channels, the accumulated particulate matter needs to be burnt off to a certain extent, and the regeneration is called. There are two methods of DPF regeneration, one is passive regeneration and one is active regeneration. The passive regeneration is carried out in the driving process, 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 congestion, poor fuel quality, component failure, or short haul transportation where the exhaust temperature does not reach the regeneration temperature. Frequent failure of passive regeneration of a DPF can result in excessive particulate matter accumulation on the DPF, resulting in increased backpressure, increased fuel consumption, and engine failure, at which point active regeneration is required. The active regeneration usually adopts in-situ parking, oil is injected into the aftertreatment system for 40 minutes to 1 hour when the engine operates in an idling mode, the temperature of tail gas is increased to 500-600 ℃, and particulate matters are combusted. The active regeneration consumes oil and time, extra cost is added for a vehicle owner, and meanwhile if the active regeneration system is controlled wrongly or fails, oil injection is excessive, the local temperature is too high, the DPF can be burned and scrapped, and larger economic loss is caused. Therefore, the successful implementation of the passive regeneration is the necessary requirement of up-to-standard emission of the diesel vehicle discharged by the VI in China.
Currently, when DPF clogging reaches a certain threshold, active regeneration cannot be completed, and only offline regeneration can be performed. The off-line regeneration is to remove the DPF from the vehicle, purge the DPF in a dedicated regeneration device using high pressure air or a particulate trap liquid in a reverse direction, wash the particulate matter, dry the DPF with hot air, and load the DPF back to the vehicle after detection. Chinese patent CN112943413A discloses a diesel vehicle DPF regeneration detection device and a detection method thereof; chinese patent CN111720190A discloses a particulate matter trapping liquid for diesel vehicle DPF regeneration device and a preparation method thereof. The technical requirement vehicle of this kind washing DPF is maintained, wastes time and energy, and easily punctures the wall flow micropore in the DPF, causes DPF filtration efficiency to reduce. Chinese patent CN104845682A discloses a fuel catalyst for internal combustion engine of automobile, which is composed of tourmaline, alumina, iron oxide and cerium oxide, and the catalyst is put into the oil inlet end of fuel filter to save oil and remove carbon deposit, but the alumina, iron oxide and cerium oxide are all particles about 250 μm, and can not be dissolved in fuel oil and the application in regeneration of DPF particle catcher is not mentioned. Chinese patent CN102125845A discloses a nano quantum dot grade diesel vehicle fuel additive catalyst, a preparation method and application thereof, trivalent cerium metal salt or a mixture of trivalent cerium and trivalent iron metal salt is added into alcohol ether, and a cerium oxide catalyst or a cerium-iron composite oxide is prepared by adopting a two-stage heating method. Although the particle size of the catalyst is below 5nm, the catalyst is still insoluble in fuel oil and nanoparticles are easy to agglomerate, so that the use of the catalyst is influenced.
Therefore, there is a need to develop a diesel additive which can be conveniently added into the fuel tank during refueling, can be uniformly mixed with fuel, can reduce the formation of particulate matters in the engine, can remarkably improve the regeneration mileage of the DPF after tail gas reaches the DPF, can shorten the regeneration time of the DPF, can reduce the number of active regeneration, can save fuel, and can reduce the maintenance number and cost of the DPF of a vehicle.
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 fuel additive containing bimetal. The fuel oil additive containing bimetal of the invention is conveniently added into the fuel oil tank when in refueling, and can be uniformly mixed with fuel oil, the formation of particulate matters is reduced in the engine, after tail gas reaches DPF, the passive regeneration failure of a diesel engine particle trap (DPF) can be effectively solved, and the active regeneration times are reduced, thereby achieving the effects of maintaining the DPF particle trap, saving oil and reducing the maintenance times and cost.
One of the purposes of the invention is to provide a preparation method of a ferrocene-porphyrin metal complex.
The method comprises the following steps:
(1) dissolving porphyrin with active hydroxyl or amido and metal salt in a solvent A, and reacting under stirring;
(2) cooling the mixture obtained in the step (1) to room temperature, pouring the mixture into ice water to generate a precipitate, and performing suction filtration, washing and drying to obtain a porphyrin metal complex;
(3) dissolving the 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 (c),
the structure of the porphyrin with active hydroxyl or amido is as follows:
R1、R2、R3the same or different, are respectively and independently selected from H, OH and NH2、Cl、Br、NO2、CnH2n+1Or OCnH2n+1Wherein n is 1-20; and/or the presence of a gas in the gas,
the metal salt is at least one of chlorides, nitrates, acetates and perchlorates of cerium, platinum, ruthenium and palladium, and preferably the chlorides, nitrates, acetates and perchlorates of cerium and platinum; and/or the presence of a gas in the gas,
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 amido to the metal salt is 1: 0.1-1: 10;
the concentration of the porphyrin with active hydroxyl or amido dissolved in the solvent A is 0.01-10 mol/L;
the concentration of the metal salt 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 hours, preferably 1-10 hours.
In a preferred embodiment of the present invention,
in the step (3), the step (c),
the ferrocene with carboxyl or aldehyde group is one or more of ferrocene monoformic acid, ferrocene dicarboxylic acid, ferrocene monoformaldehyde and ferrocene dicarboxaldehyde; and/or the presence of a gas in the gas,
the solvent B is at least one of dichloromethane, dichloroethane and chloroform; and/or the presence of a gas in the atmosphere,
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, 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 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, respectively;
the reaction temperature is preferably 0-60 ℃ under the reflux condition, and the reaction time is 0.5-20 h, preferably 5-20 h.
The second purpose of the invention is to provide a ferrocene-porphyrin metal complex prepared by the method of the first purpose of the invention.
The third purpose of the invention is to provide a fuel additive containing bimetal, which comprises the ferrocene-porphyrin metal complex of the second purpose of the invention.
The fuel additive is prepared from components including solvent naphtha, amine detergent and the ferrocene-porphyrin metal complex;
the components are calculated according to the parts by weight,
100 parts of solvent oil;
0.1-30 parts of amine detergent; preferably 10 to 20 parts by weight; more preferably 10 to 15 parts by weight;
0.01-15 parts by weight of ferrocene-porphyrin metal complex; preferably 1 to 5 parts by weight.
In a preferred embodiment of the present invention,
the fuel oil additive can also be added with an antioxidant.
In a preferred embodiment of the present invention,
based on 100 parts by weight of the solvent oil,
0.1-1.5 parts by weight of an 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 solvent oil and is used for dissolving each component in the additive; and/or the presence of a gas in the gas,
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, discharging the carbon deposition along with waste gas and trapping the carbon deposition by a particle trap; and/or the presence of a gas in the gas,
the antioxidant can be conventional antioxidant in the prior art, and in the present invention, phenylenediamine, alkyl phenylenediamine, p-tert-butylphenol or 2, 6-di-tert-butyl-p-cresol (BHT) can be preferably used.
The fuel additive of the invention can also be added with conventional components in the field, such as polyether, and the dosage of the conventional components is also conventional, and the technical personnel can adjust the conventional components according to the actual situation.
The fourth purpose of the invention is to provide a preparation method of the fuel additive containing bimetal, which is the third purpose of the invention.
The method comprises the following steps:
and uniformly mixing the components according to the using amount to obtain the fuel oil additive containing the bimetal.
The fifth purpose of the invention is to provide the application of the fuel additive of the third purpose of the invention or the fuel additive prepared by the method of the fourth purpose of the invention in the regeneration of the diesel particulate filter.
The fuel additive is blended with fuel 1/1000-1/20 according to the proportion for use.
The invention can adopt the following specific technical scheme:
the preparation method of the ferrocene-porphyrin metal complex preferably comprises the following steps: dissolving porphyrin with active hydroxyl or amido and metal salt in a solvent A, wherein the concentration of the porphyrin is 0.01-10 mol/L, 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 hours under magnetic stirring; thirdly, cooling the reaction mixture to room temperature, pouring the reaction mixture into ice water to generate precipitate, and performing suction filtration, washing and drying to obtain the porphyrin metal complex; dissolving the porphyrin metal complex and the ferrocene with carboxyl or aldehyde group obtained in the third step in a solvent B, adding tertiary amine, and reacting for 0.5-20 h at 0-60 ℃, wherein the concentration of the porphyrin metal complex is 0.01-10 mol/L, and the concentration of the ferrocene with carboxyl or aldehyde group is 0.01-10 mol/L; and fifthly, evaporating the solvent of the reaction mixture obtained in the fourth step to obtain the ferrocene-porphyrin metal complex.
The preparation method of the fuel oil additive containing the bimetal preferably comprises the step 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 the temperature of 20-60 ℃ to prepare the fuel oil additive containing the bimetal.
The invention has the following beneficial effects:
under normal working conditions of a conventional diesel vehicle, the exhaust temperature is 200-400 ℃, the ignition point of particles is often as high as 450 ℃, and the passive regeneration of the trap is difficult to realize; after the DPF regeneration additive is added into fuel oil, the fuel oil and the catalyst are mixed and combusted, formed PM is closely adhered with the metal catalyst, and the temperature for PM combustion (namely the temperature for PM accumulation and regeneration on the DPF to reach balance) is reduced.
The fuel oil additive containing the bimetal is used by blending the additive and fuel oil 1/1000-1/20 according to the proportion when in use, has good solubility, can effectively solve the problem of failure of passive regeneration of the DPF particle trap of a diesel engine, and reduces the number of active regeneration, thereby achieving the effects of maintaining the DPF particle trap, saving oil and reducing the number of maintenance times and cost.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples are all conventional commercially available raw materials.
Equilibrium point temperature test reference standard: the technical requirements of the T/CAEPI 12.3-2017 diesel vehicle exhaust aftertreatment device are as follows: a diesel particulate trap (DPF).
Example 1
Preparation of porphyrin metal complex (cerium porphyrin): dissolving 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50mmol) and cerium acetate (150mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 150 ℃ under magnetic stirring for reaction for 8h, pouring the reaction mixed solution into ice water to separate out cerium porphyrin, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the porphyrin-cerium complex with active hydroxyl.
Preparation of ferrocene-porphyrin cerium complex: dissolving 20mmol of porphyrin cerium metal complex with 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.
Preparing a fuel additive containing ferrocene-porphyrin cerium complex: 1.1 parts by weight of ferrocene-porphyrin cerium complex, 11.3 parts by weight of polyisobutylene succinimide, 100 parts by weight of No. 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-porphyrin cerium complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-porphyrin cerium complex bimetal is mixed with fuel according to the volume ratio of 1:10, the dispersion is good, and the mixture is placed for 12 months without layering and precipitation.
The performance of the fuel additive containing the ferrocene-porphyrin cerium complex is as follows: the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising a DOC, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:800, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 316 ℃, and is reduced by 84 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; 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, the average value of air flow loss is 26.3% when the lift of a 1-4 cylinder needle valve is 0.1mm, and the result shows that the fuel additive containing the ferrocene-porphyrin cerium complex has an excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. In the test process, a fuel additive containing ferrocene-porphyrin cerium 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, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the fuel additive containing the ferrocene-porphyrin cerium complex is added, the DPF triggers regeneration when the vehicle actually travels about 5000 kilometers, so that the DPF regeneration interval mileage is greatly prolonged.
Example 2
Preparation of porphyrin metal complex (platinum porphyrin): dissolving monoamino tetraphenyl porphyrin (400mmol) and platinum chloride (200mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 120 ℃ under magnetic stirring for reaction for 2h, pouring the reaction mixed solution into ice water to separate out a product, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the monoamino tetraphenyl porphyrin-platinum complex.
Preparation of ferrocene-porphyrin platinum complex: dissolving 200mmol of monoamino tetraphenylporphyrin-platinum metal complex and 400mmol of ferrocenedicarboxylic acid in 50mL of dichloroethane, adding 2mL of triethylamine, reacting for 16h under a reflux condition, and evaporating the solvent after the reaction is finished to obtain the ferrocene-porphyrin platinum complex.
The preparation of the bimetallic fuel additive containing the ferrocene-porphyrin platinum complex comprises the following steps: 2.3 parts of ferrocene-porphyrin platinum complex, 14 parts of polyisobutene amine, 100 parts of No. 120 solvent oil and 0.6 part of antioxidant BHT are uniformly mixed at 50 ℃ to prepare the bimetallic fuel oil 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 dispersion is good, and the fuel additive is placed for 12 months without layering and precipitation.
The performance of the fuel additive containing the ferrocene-porphyrin platinum complex is as follows: bench test is carried out by adopting a Weichai WP13 heavy diesel engine, and the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising DOCs, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the ferrocene-porphyrin platinum complex is added into the diesel according to the volume ratio of 1:100, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 309 ℃ and reduced by 91 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; after the fuel additive containing the ferrocene-porphyrin platinum complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000, the average value of air flow loss is 23.5 percent when the lift of the 1-4 cylinder needle valve is 0.1mm, and the result shows that the fuel additive containing the ferrocene-porphyrin platinum complex has an excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. 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, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the fuel additive containing ferrocene-porphyrin platinum complex is added, the DPF triggers regeneration when the vehicle actually travels about 5500 kilometers, so that the DPF regeneration interval mileage is greatly prolonged.
Example 3
Preparation of porphyrin metal complex (cerium porphyrin): dissolving 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50mmol) and cerium acetate (150mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 150 ℃ under magnetic stirring for reaction for 8h, pouring the reaction mixed solution into ice water to separate out cerium porphyrin, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the porphyrin-cerium complex with active hydroxyl.
Preparation of ferrocene-porphyrin cerium complex: dissolving 20mmol of porphyrin cerium metal complex with 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.
Preparing a fuel additive containing ferrocene-porphyrin cerium complex: 5.0 parts of ferrocene-porphyrin cerium complex, 11.3 parts of polyisobutylene succinimide, 100 parts of No. 6 solvent oil and 0.6 part of p-phenylenediamine by weight are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene-porphyrin cerium complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-porphyrin cerium complex bimetal is mixed with fuel according to the volume ratio of 1:10, the dispersion is good, and the mixture is placed for 12 months without layering and precipitation.
The performance of the fuel additive containing the ferrocene-porphyrin cerium complex is as follows: the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising a DOC, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the change in differential pressure across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:300, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 306 ℃, and is reduced by 94 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; 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, the average value of air flow loss in a time and space of 0.1mm of the lift of a 1-4 cylinder needle valve is 23.0 percent, and the result shows that the fuel additive containing the ferrocene-porphyrin cerium complex has an excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. In the test process, a fuel additive containing ferrocene-porphyrin cerium 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, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the fuel additive containing the ferrocene-porphyrin cerium complex is added, the DPF triggers regeneration when the vehicle actually travels about 5500 kilometers, so that the DPF regeneration interval mileage is greatly prolonged.
Example 4
Preparation of porphyrin metal complex (cerium porphyrin): dissolving 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50mmol) and cerium acetate (150mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 150 ℃ under magnetic stirring for reaction for 8h, pouring the reaction mixed solution into ice water to separate out cerium porphyrin, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the porphyrin-cerium complex with active hydroxyl.
Preparation of ferrocene-porphyrin cerium complex: dissolving 20mmol of porphyrin cerium metal complex with 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.
Preparing a fuel additive containing ferrocene-porphyrin cerium complex: 3.5 parts of ferrocene-porphyrin cerium complex, 11.3 parts of polyisobutylene succinimide, 100 parts of No. 6 solvent oil and 0.6 part of p-phenylenediamine by weight are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene-porphyrin cerium complex bimetal.
Solubility of fuel additive containing ferrocene-porphyrin cerium complex bimetal: after the fuel additive containing ferrocene-porphyrin cerium complex bimetal is mixed with fuel according to the volume ratio of 1:10, the dispersion is good, and the mixture is placed for 12 months without layering and precipitation.
The performance of the fuel additive containing the ferrocene-porphyrin cerium complex is as follows: bench tests are carried out by adopting a Weichai WP13 heavy-duty diesel engine, and the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising DOCs, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the ferrocene-porphyrin cerium complex is added into diesel according to the volume ratio of 1:500, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 314 ℃ and is reduced by 86 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; 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, the average value of air flow loss is 25.4% when the lift of a 1-4 cylinder needle valve is 0.1mm, and the result shows that the fuel additive containing the ferrocene-porphyrin cerium complex has an excellent effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. In the test process, a fuel additive containing ferrocene-porphyrin cerium 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, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the fuel additive containing the ferrocene-porphyrin cerium complex is added, the DPF triggers regeneration when the vehicle actually travels about 5000 kilometers, so that the DPF regeneration interval mileage is greatly prolonged.
Example 5
Preparation of porphyrin metal complex (platinum porphyrin): dissolving monoamino tetraphenyl porphyrin (400mmol) and platinum chloride (200mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 120 ℃ under magnetic stirring for reaction for 2h, pouring the reaction mixed solution into ice water to separate out a product, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the monoamino tetraphenyl porphyrin-platinum complex.
Preparation of ferrocene-porphyrin platinum complex: dissolving 200mmol of monoamino tetraphenylporphyrin-platinum metal complex and 400mmol of ferrocene dicarboxylic acid in 50mL of dichloroethane, adding 2mL of triethylamine, reacting for 16h under a reflux condition, and evaporating the solvent after the reaction is finished to obtain the ferrocene-porphyrin platinum complex.
The preparation of the bimetallic fuel additive containing the ferrocene-porphyrin platinum complex comprises the following steps: 5.0 parts of ferrocene-porphyrin platinum complex, 14 parts of polyisobutene amine, 100 parts of No. 120 solvent oil and 0.6 part 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 dispersion is good, and the fuel additive is placed for 12 months without layering and precipitation.
The performance of the fuel additive containing the ferrocene-porphyrin platinum complex is as follows: the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising a DOC, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the ferrocene-porphyrin platinum complex is added into the diesel according to the volume ratio of 1:500, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 302 ℃, and is reduced by 98 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; after the fuel additive containing the ferrocene-porphyrin platinum complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000, the average value of the air flow loss is 21.3 percent when the lift of the needle valve of a 1-4 cylinder is 0.1mm, which shows that 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 to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. 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, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the fuel additive containing ferrocene-porphyrin platinum complex is added, the DPF triggers regeneration when the vehicle actually travels about 5500 kilometers, so that the DPF regeneration interval mileage is greatly prolonged.
Comparative example 1
Preparation of porphyrin metal complex (cerium porphyrin): dissolving 5,10,15, 20-tetra (4-hydroxyphenyl) porphyrin (50mmol) and cerium acetate (150mmol) in N' N-dimethylformamide (50mL), heating the reaction system to 150 ℃ under magnetic stirring for reaction for 8h, pouring the reaction mixed solution into ice water to separate out cerium porphyrin, performing suction filtration, washing with deionized water, and performing vacuum drying to obtain the porphyrin-cerium complex with active hydroxyl.
Preparation of the fuel additive containing the porphyrin cerium complex: 1.1 parts of porphyrin cerium complex, 11.3 parts of polyisobutylene succinimide, 100 parts of No. 6 solvent oil and 0.6 part of p-phenylenediamine by weight are uniformly mixed at 30 ℃ to prepare the fuel additive containing the porphyrin cerium complex.
The performance of the fuel additive containing the porphyrin cerium complex is as follows: the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising a DOC, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing the porphyrin cerium complex is added into the diesel according to the volume ratio of 1:800, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 345 ℃ and is reduced by 55 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764-; after the fuel additive containing the porphyrin cerium complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000, the average value of air flow loss in a 1-4 cylinder needle valve with the lift of 0.1mm is 29.7 percent, and the result shows that the fuel additive containing the porphyrin cerium has a certain effect of removing carbon deposition of an engine.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. In the test process, the fuel additive containing the porphyrin cerium complex is added into the diesel oil, and the adding concentration is 10mg/kg (based on the cerium content). Before the test, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, and after the cerium porphyrin-containing fuel additive is added, the DPF triggers regeneration when the vehicle actually travels about 3000 kilometers, so that the DPF regeneration interval mileage is prolonged.
Comparative example 2
Preparation of ferrocene-containing fuel additive: 1.1 parts of ferrocene, 11.3 parts of polyisobutylene succinimide, 100 parts of No. 6 solvent oil and 0.6 part of p-phenylenediamine by weight are uniformly mixed at 30 ℃ to prepare the fuel additive containing the ferrocene.
Performance of ferrocene-containing fuel additive: the bench test device comprises a diesel engine, a dynamometer, an aftertreatment device system comprising a DOC, a particulate trap (DPF) and an SCR and a data acquisition system. The DPF deposit balance point temperature is measured by adjusting the engine operating point to adjust the exhaust temperature, starting at 300 ℃ and ending at each 20 ℃ increase to 440 ℃. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change across the DPF. For the same aftertreatment device (DPF comprises a catalyst coating), before adding the fuel additive, the temperature of the equilibrium point is 400 ℃, the fuel additive containing ferrocene is added into diesel according to the volume ratio of 1:800, and after adding the fuel additive, the temperature of the equilibrium point is reduced to 353 ℃ and reduced by 47 ℃.
Nozzle coking detection is carried out according to the method and technical requirements specified in SH/T0764 diesel engine nozzle coking test method (XUD-9 method), and the average loss value of air flow is 85.5% when the lift of a fuel 1-4 cylinder needle valve without fuel additive is 0.1 mm; after the fuel additive containing ferrocene is added according to the volume ratio of 1:1000 of the fuel additive to the fuel, the average value of the loss of air flow is 30.3 percent when the lift of the 1-4 cylinder needle valve is 0.1mm, and the carbon deposit of the engine can be removed to a certain extent.
A small truck carrying a 2.0LCTI diesel engine is adopted to carry out a real-time test, the volume of the DPF of the vehicle is 3.3L, the maximum carbon loading capacity is calibrated to be 20g, and the regeneration interval driving distance of the whole vehicle is about 500 km. In the test process, the fuel oil additive containing ferrocene is added into diesel oil, and the addition concentration is 10mg/kg (based on the iron content). Before the test, after the vehicle is estimated to travel about 400 kilometers again, the DPF triggers regeneration, after the fuel additive containing ferrocene is added, the DPF triggers regeneration when the vehicle actually travels about 1500 kilometers, and the DPF regeneration interval mileage is slightly prolonged.
From examples 1 to 5 it can be seen that: on one hand, compared with the fuel additive only containing porphyrin metal complex or ferrocene, the fuel additive can effectively reduce the temperature of a balance point, thereby effectively solving the problem that the DPF particle trap of a diesel engine fails in passive regeneration, reducing the number of active regeneration times, prolonging the regeneration mileage and achieving the effects of maintaining the DPF particle trap, saving oil and reducing the number of maintenance times and cost; 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 keep stable for a long time after mixing.
As can be seen from comparative examples 1-2 and example 1: the fuel additive of embodiment 1 contains the ferrocene-porphyrin cerium complex, and 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 of failure of passive regeneration of the DPF particle trap of the diesel engine, reducing the number of active regeneration, prolonging the regeneration mileage, and achieving the effects of maintaining the DPF particle trap, saving oil and reducing the maintenance number and cost.
Claims (10)
1. A preparation method of ferrocene-porphyrin metal complex is characterized by comprising the following steps:
(1) dissolving porphyrin with active hydroxyl or amido and metal salt in a solvent A, and reacting under stirring;
(2) cooling the mixture obtained in the step (1) to room temperature, pouring the mixture into ice water to generate a precipitate, and performing suction filtration, washing and drying to obtain a porphyrin metal complex;
(3) dissolving the 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.
2. The method of claim 1, wherein:
in the step (1), the step (c),
the structure of the porphyrin with active hydroxyl or amido is as follows:
R1、R2、R3the same or different, are respectively and independently selected from H, OH and NH2、Cl、Br、NO2、CnH2n+1Or OCnH2n+1Wherein n is 1-20; and/or the presence of a gas in the gas,
the metal salt is at least one of chloride, nitrate, acetate and perchlorate of cerium, platinum, ruthenium and palladium; and/or the presence of a gas in the gas,
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 amido to the metal salt is 1: 0.1-1: 10;
the concentration of the porphyrin with active hydroxyl or amido dissolved in the solvent A is 0.01-10 mol/L;
the concentration of the metal salt 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 method of claim 1, wherein:
in the step (3), the step (c),
the ferrocene with carboxyl or aldehyde group is one or more of ferrocene monoformic acid, ferrocene dicarboxylic acid, ferrocene monoformaldehyde and ferrocene dicarboxaldehyde; and/or the presence of a gas in the gas,
the solvent B is at least one of dichloromethane, dichloroethane and chloroform; and/or the presence of a gas in the gas,
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 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, respectively;
the reaction time is 0.5-20 h.
4. A ferrocene-porphyrin metal complex as prepared by the method as defined in any one of claims 1 to 3.
5. A fuel additive containing a bimetal comprising the ferrocene-porphyrin metal complex as recited in claim 4, wherein:
the fuel additive is prepared from components including solvent naphtha, amine detergent and the ferrocene-porphyrin metal complex;
the components are calculated according to the parts by weight,
100 parts of solvent oil;
0.1-30 parts by weight of amine detergent;
0.01-15 parts by weight of ferrocene-porphyrin metal complex.
6. The fuel additive of claim 5 wherein:
100 parts of solvent oil;
10-20 parts of amine detergent;
1-5 parts of ferrocene-porphyrin metal complex.
7. The fuel additive of claim 5 wherein:
the fuel oil additive can also be added with an antioxidant.
8. The fuel additive of claim 5 wherein:
the solvent oil is at least one of alkane solvent oil and aromatic solvent oil; and/or the presence of a gas in the gas,
the amine detergent is at least one of polyisobutylene succinimide, polyisobutylene amine and polyether amine.
9. A method of producing a fuel additive according to any one of claims 5 to 8, wherein the method comprises:
and uniformly mixing the components according to the using amount to obtain the fuel oil additive containing the bimetal.
10. Use of a fuel additive according to any one of claims 5 to 8 or prepared by the method of claim 9 in the regeneration of a diesel particulate trap, wherein:
the fuel additive is blended with fuel 1/1000-1/20 according to the proportion for use.
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