CN114317046B - Fuel additive containing crown ether metal complex and preparation method and application thereof - Google Patents
Fuel additive containing crown ether metal complex and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fuel additive containing crown ether metal complex, a preparation method and application thereof. The fuel additive containing the crown ether metal complex can effectively reduce the temperature of a balance point, remove carbon deposition of an engine, effectively solve the problem that a DPF particle catcher of a diesel engine fails to passively regenerate, reduce the number of active regeneration and prolong the regeneration mileage, thereby achieving the effects of maintaining the DPF particle catcher, saving oil and reducing the maintenance number and cost; in addition, 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, so that the fuel additive disclosed by the invention has good solubility in fuel.
Description
Technical Field
The invention belongs to the technical field of fuel additives, and particularly relates to a fuel additive containing crown ether metal complex, and a preparation method and application thereof.
Background
The DPF of the diesel vehicle is used as an effective device for reducing the emission of particulate matters, 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 requirement of the emission standard of the particulate matters, and the DPF of the diesel vehicle can not meet the emission requirement only by adding the DPF of the particulate matter.
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. 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 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. 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.
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
The invention provides a fuel additive containing crown ether metal complex, a preparation method and application thereof, and aims to solve the problems in the prior art. The fuel additive containing the crown ether metal complex can be conveniently added into an oil tank during oiling, can be uniformly mixed with fuel, reduces the formation of particulate matters in an engine, can obviously improve DPF regeneration mileage after tail gas reaches a DPF, shortens DPF regeneration time, reduces active regeneration times, saves fuel, and reduces the maintenance times and cost of a vehicle DPF.
The invention aims at providing a fuel additive containing crown ether metal complex.
The fuel additive is prepared from components including solvent oil, an amine detergent and a crown ether 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 5 to 15 parts by weight;
0.01 to 15 parts by weight of crown ether metal complex; preferably 0.1 to 5 parts by weight.
In a preferred embodiment of the present invention,
the crown ether metal complex is prepared from raw materials including crown ether, metal salt, a solvent A and a solvent B, and the crown ether metal complex is a main catalyst component.
The preparation method of the crown ether metal complex comprises the following steps: (1) Dissolving crown ether in a solvent A to prepare crown ether solution; (2) Dissolving metal salt in a solvent B to prepare a salt solution; (3) And mixing the crown ether solution with the salt solution for reaction, and standing for layering or filtering and drying to obtain the crown ether metal complex.
In a preferred embodiment of the present invention,
the crown ether is at least one of aza-15-crown ether-5, benzo-15-crown-5-ether, dibenzo-15-crown ether-5, 18-crown-6 ether, benzo-18-crown-6-ether, dibenzo-18-crown ether-6, 21-crown ether-7, benzo-21-crown-7-ether, dibenzo-21-crown 7-ether, 24-crown-8-ether, benzo-24-crown-8-ether, dibenzo-24-crown ether-8 and nitro, amino, hydroxyl, carboxyl and alkylation derivatives thereof; and/or the number of the groups of groups,
the metal salt is at least one of chloride, nitrate and perchlorate of potassium, calcium, magnesium, iron, cerium, platinum and palladium, preferably chloride, nitrate, acetate and perchlorate of iron, cerium and platinum, more 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 chloroform, dichloromethane, dichloroethane and carbon tetrachloride; and/or the number of the groups of groups,
the solvent B is at least one of acetonitrile, ethanol and water.
In a preferred embodiment of the present invention,
the solvent oil boiling range is 60-200 ℃, and is preferably at least one of alkane solvent oil and aromatic hydrocarbon solvent oil, so as to dissolve each component in the additive.
In a preferred embodiment of the present invention,
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.
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 0.1 to 1 part by weight.
In a preferred embodiment of the present invention,
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 second purpose of the invention is to provide a preparation method of the fuel additive which is one of the purposes of the invention.
The method comprises the following steps:
and uniformly mixing the components according to the dosage to obtain the fuel additive containing the crown ether metal complex.
It is a further object of the present invention to provide the use of a fuel additive according to one of the objects of the present invention or a fuel additive prepared by a method according to the second object of the present invention for regenerating 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 crown ether metal complex comprises the following steps: firstly, crown ether is dissolved in chloroform, dichloromethane, dichloroethane or carbon tetrachloride to prepare 0.01-10 mol/L crown ether solution; secondly, dissolving chlorides, nitrates or perchlorates of potassium, calcium, magnesium, iron, cerium, platinum or palladium in acetonitrile, ethanol, water or a mixture thereof to prepare a salt solution with the concentration of 0.01-10 mol/L; thirdly, mixing the crown ether solution in the first step and the salt solution in the second step, wherein the molar ratio of porphyrin to metal salt is 1:0.1-1:10 after mixing, and placing the mixture in a constant-temperature water bath oscillator for oscillating for 1-12 hours at the temperature of 20-50 ℃ and the rpm of 50-500 rpm; and fourthly, standing the mixture obtained in the third step for layering or filtering, evaporating the organic phase to remove the solvent to obtain the crown ether metal complex or drying the filtered filter residues to obtain the crown ether metal complex.
The preparation method of the fuel additive containing crown ether metal complex comprises the following steps: the fuel additive containing the crown ether metal complex is prepared by uniformly mixing 0.01-15 parts by weight of crown ether 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 ℃.
The principle of the invention is as follows:
crown ether is used as a carrier to complex metal ions, so that the crown ether can be well dissolved in fuel oil; in addition, the crown ether metal complex can be used as an oxidation catalyst to catalyze the fuel oil oxidation under the action of light or heat, so that the equilibrium point temperature is reduced.
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 beneficial effects of the invention are as follows:
the fuel additive containing crown ether metal complex is used by blending the additive and fuel in a ratio 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, reduces active regeneration times, prolongs regeneration time and regeneration distance, and reduces average oil consumption, 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 crown ether metal complex (benzo 18 crown 6-Fe): firstly, dissolving benzo-18-crown-6-ether in chloroform to prepare 0.5mol/L crown ether solution; secondly, dissolving ferric nitrate in ethanol to prepare a ferric salt solution with the concentration of 0.5 mol/L; thirdly, mixing the benzo-18-crown-6-ether solution in the first step and the ferric salt solution in the second step according to the volume ratio of 1:1, and placing the mixture in a constant temperature water bath oscillator to oscillate for 8 hours at 30 ℃ and 200 rpm; and (3) filtering the mixture obtained in the third step, and drying filter residues to obtain the benzo 18 crown 6-Fe metal complex.
Preparation of fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe): 2.5 parts by weight of benzo 18 crown 6-Fe complex, 6 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 50 ℃ to prepare the fuel additive containing the benzo 18 crown 6-Fe complex.
Solubility of fuel additives containing crown ether metal complexes (benzo 18 crown 6-Fe): after the fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe) and fuel oil are mixed according to the volume ratio of 1:10, the dispersion is good, and the fuel additive is placed for 12 months, and has no layering and no precipitation.
Properties of fuel additives containing crown ether metal complexes: 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 including catalyst coating), the equilibrium point temperature is 400 ℃ before adding the fuel additive, the fuel additive containing the benzo 18 crown 6-Fe complex is added into diesel oil according to the volume ratio of 1:100, and after adding the fuel additive, the equilibrium point temperature is reduced to 310 ℃ and reduced by 90 ℃.
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 in the lift of the needle valve of the 1-4 cylinder after the fuel additive containing the benzo 18 crown 6-Fe complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000 is 24.0 percent, which shows that the fuel additive containing the benzo 18 crown 6-Fe complex has excellent effect of removing carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, a fuel additive containing benzo 18 crown 6-Fe complex is added into diesel oil, and the addition concentration is 10mg/kg (calculated by iron content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel for about 400 km, and DPF triggers regeneration after the fuel additive containing the benzo 18 crown 6-Fe complex is added, so that DPF regeneration interval mileage is greatly prolonged after the DPF actually travels for about 4500 km.
Example 2
Preparation of crown ether metal complex (dibenzo 21 crown 7-Ce): firstly, dissolving dibenzo-21-crown 7-ether in chloroform to prepare crown ether solution with the concentration of 0.5 mol/L; secondly, dissolving cerium nitrate in water to prepare 0.5mol/L cerium salt solution; thirdly, mixing the dibenzo-21-crown 7-ether solution in the first step and the cerium salt solution in the second step according to the volume ratio of 1:1, and placing the mixture in a constant-temperature water bath oscillator to oscillate for 12 hours at 30 ℃ and 200 rpm; and (3) filtering the mixture obtained in the third step, and drying filter residues to obtain the dibenzo 21 crown 7-Ce metal complex.
Preparation of fuel additive containing crown ether metal complex (dibenzo 21 crown 7-Ce): 4.7 parts by weight of dibenzo 21 crown 7-Ce complex, 11.7 parts by weight of polyisobutene amine, 100 parts by weight of 120# solvent oil and 0.6 part by weight of BHT are uniformly mixed at 30 ℃ to prepare the fuel additive containing the dibenzo 21 crown 7-Ce complex.
Solubility of fuel additive containing crown ether metal complex (dibenzo 21 crown 7-Ce): after the fuel additive containing crown ether metal complex (dibenzo 21 crown 7-Ce) and fuel oil are mixed according to the volume ratio of 1:50, the dispersion is good, and the fuel additive is placed for 12 months without layering or precipitation.
Properties of fuel additives containing crown ether metal complexes (dibenzo 21 crown 7-Ce): 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 dibenzo 21 crown 7-Ce complex is added into diesel oil according to the volume ratio of 1:500, and the temperature of the balance point is reduced by 330 ℃ after the fuel additive is added, and the temperature is reduced by 70 ℃.
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 benzo 21 crown 7-Ce complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 25.0%, which shows that the fuel additive containing the benzo 21 crown 7-Ce complex has excellent effect of removing carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, the fuel additive containing dibenzo 21 crown 7-Ce complex is added into diesel oil with the addition concentration of 10mg/kg (calculated by cerium content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel for about 400 km, and DPF triggers regeneration after the fuel additive containing dibenzo 21 crown 7-Ce complex is added, so that DPF regeneration interval mileage is greatly prolonged after the vehicle actually travels for about 4500 km.
Example 3
Preparation of crown ether metal complex (benzo 15 crown 5-Fe): firstly, dissolving benzo-15-crown-5-ether in chloroform to prepare 0.5mol/L crown ether solution; secondly, dissolving ferric nitrate in ethanol to prepare a ferric salt solution with the concentration of 0.5 mol/L; thirdly, mixing the benzo-15-crown-5-ether solution in the first step and the ferric salt solution in the second step according to the volume ratio of 1:1, and placing the mixture in a constant temperature water bath oscillator to oscillate for 8 hours at 30 ℃ and 200 rpm; and (3) filtering the mixture obtained in the third step, and drying filter residues to obtain the benzo 15 crown 5-Fe metal complex.
Preparation of fuel additive containing crown ether metal complex (benzo 15 crown 5-Fe): 5 parts by weight of benzo 15 crown 5-Fe complex, 10 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 50 ℃ to prepare the fuel additive containing the benzo 15 crown 5-Fe complex.
Solubility of fuel additives containing crown ether metal complexes (benzo 15 crown 5-Fe): after the fuel additive containing crown ether metal complex (benzo 15 crown 5-Fe) and fuel oil are mixed according to the volume ratio of 1:50, the dispersion is good, and the fuel additive is placed for 12 months, and has no layering and no precipitation.
Properties of fuel additives containing crown ether metal complexes: 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 including catalyst coating), the equilibrium point temperature is 400 ℃ before adding the fuel additive, the fuel additive containing the benzo 15 crown 5-Fe complex is added into diesel oil according to the volume ratio of 1:400, and after adding the fuel additive, the equilibrium point temperature is reduced to 326 ℃ and is reduced by 74 ℃.
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 in the needle valve lift of 1-4 cylinders after the fuel additive containing the benzo 15 crown 5-Fe complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 25.4 percent, which shows that the fuel additive containing the benzo 15 crown 5-Fe complex has excellent effect of removing the carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, a fuel additive containing benzo 15 crown 5-Fe was added to diesel oil at a concentration of 10mg/kg (based on iron content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel for about 400 km, and DPF triggers regeneration after the fuel additive containing the benzo 15 crown 5-Fe complex is added, so that DPF regeneration interval mileage is greatly prolonged after the DPF actually travels for about 4000 km.
Example 4
Preparation of crown ether metal complex (benzo 18 crown 6-Fe): firstly, dissolving benzo-18-crown-6-ether in chloroform to prepare 0.5mol/L crown ether solution; secondly, dissolving ferric nitrate in ethanol to prepare a ferric salt solution with the concentration of 0.5 mol/L; thirdly, mixing the benzo-18-crown-6-ether solution in the first step and the ferric salt solution in the second step according to the volume ratio of 1:1, and placing the mixture in a constant temperature water bath oscillator to oscillate for 8 hours at 30 ℃ and 200 rpm; and (3) filtering the mixture obtained in the third step, and drying filter residues to obtain the benzo 18 crown 6-Fe metal complex.
Preparation of fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe): 5 parts by weight of benzo 18 crown 6-Fe complex, 6 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 50 ℃ to prepare the fuel additive containing the benzo 18 crown 6-Fe complex.
Solubility of fuel additives containing crown ether metal complexes (benzo 18 crown 6-Fe): after the fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe) and fuel oil are mixed according to the volume ratio of 1:10, the dispersion is good, and the fuel additive is placed for 12 months, and has no layering and no precipitation.
Properties of fuel additives containing crown ether metal complexes: 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 including catalyst coating), the equilibrium point temperature is 400 ℃ before adding the fuel additive, the fuel additive containing the benzo 18 crown 6-Fe complex is added into diesel oil according to the volume ratio of 1:500, and after adding the fuel additive, the equilibrium point temperature is reduced to 323 ℃ and is reduced by 77 ℃.
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 in the needle valve lift of 1-4 cylinders after the fuel additive containing the benzo 18 crown 6-Fe complex is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 22.6 percent, which shows that the fuel additive containing the benzo 18 crown 6-Fe complex has excellent effect of removing the carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, a fuel additive containing benzo 18 crown 6-Fe complex is added into diesel oil, and the addition concentration is 10mg/kg (calculated by iron content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel for about 400 km, and DPF triggers regeneration after the fuel additive containing the benzo 18 crown 6-Fe complex is added, so that DPF regeneration interval mileage is greatly prolonged after the DPF actually travels for about 5000 km.
Example 5
Preparation of crown ether metal complex (benzo 18 crown 6-Fe): firstly, dissolving benzo-18-crown-6-ether in chloroform to prepare 0.5mol/L crown ether solution; secondly, dissolving ferric nitrate in ethanol to prepare a ferric salt solution with the concentration of 0.5 mol/L; thirdly, mixing the benzo-18-crown-6-ether solution in the first step and the ferric salt solution in the second step according to the volume ratio of 1:1, and placing the mixture in a constant temperature water bath oscillator to oscillate for 8 hours at 30 ℃ and 200 rpm; and (3) filtering the mixture obtained in the third step, and drying filter residues to obtain the benzo 18 crown 6-Fe metal complex.
Preparation of fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe): 8 parts by weight of a benzo 18 crown 6-Fe complex, 6 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 50 ℃ to prepare the fuel additive containing the benzo 18 crown 6-Fe complex.
Solubility of fuel additives containing crown ether metal complexes (benzo 18 crown 6-Fe): after the fuel additive containing crown ether metal complex (benzo 18 crown 6-Fe) and fuel oil are mixed according to the volume ratio of 1:10, the dispersion is good, and the fuel additive is placed for 12 months, and has no layering and no precipitation.
Properties of fuel additives containing crown ether metal complexes: 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 including catalyst coating), the equilibrium point temperature is 400 ℃ before adding the fuel additive, the fuel additive containing the benzo 18 crown 6-Fe complex is added into diesel oil according to the volume ratio of 1:250, and after adding the fuel additive, the equilibrium point temperature is reduced to 318 ℃ and is reduced by 82 ℃.
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 in the lift of the needle valve of the 1-4 cylinder after the fuel additive containing the benzo 18 crown 6-Fe complex is added according to the volume ratio of the fuel additive to the fuel of 1:1000 is 21.7 percent, which shows that the fuel additive containing the benzo 18 crown 6-Fe complex has excellent effect of removing the carbon deposit of the engine.
A small truck with a 2.0L CTI 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. During the test, a fuel additive containing benzo 18 crown 6-Fe complex is added into diesel oil, and the addition concentration is 10mg/kg (calculated by iron 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 the benzo 18 crown 6-Fe complex is added, so that DPF regeneration interval mileage is greatly prolonged after the DPF actually travels about 5500 km.
Comparative example 1
Preparation of fuel additive: 5.6 parts by weight of cerium naphthenate, 11.7 parts by weight of polyisobutylene succinimide, 100 parts by weight of 120# solvent oil and 0.6 part by weight of BHT are uniformly mixed at 30 ℃ to prepare the fuel additive containing cerium naphthenate.
Properties of the fuel additive containing cerium naphthenate: 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 fuel additive containing cerium naphthenate is added into diesel oil according to the volume ratio of 1:500, and after the fuel additive is added, the equilibrium point temperature is reduced to 360 ℃ and is reduced by 40 ℃.
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 needle valve lift of the 1-4 cylinders after the fuel additive containing cerium naphthenate is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 25.5 percent, and the diesel oil has better effect on removing carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, the fuel additive containing cerium naphthenate 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 the DPF triggers regeneration after the fuel additive containing cerium naphthenate is added, thereby having a certain effect on prolonging the DPF regeneration interval mileage after the DPF actually travels about 2500 km.
Comparative example 2
Preparation of fuel additive: 6.1 parts by weight of iron oleate, 6 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 50 ℃ to prepare the fuel additive containing iron oleate.
Performance of 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), before the fuel additive is added, the equilibrium point temperature is 400 ℃, the fuel additive containing iron oleate is added into diesel oil according to the volume ratio of 1:100, and after the fuel additive is added, the equilibrium point temperature is reduced by 350 ℃ and is reduced by 50 ℃.
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 a 1-4 cylinder after the fuel additive containing ferric oleate is added according to the volume ratio of the fuel additive to the fuel oil of 1:1000 is 31.2%, and the fuel additive has a certain effect of removing carbon deposit of an engine.
A small truck with a 2.0L CTI 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. During the test, a fuel additive containing ferric oleate is added into diesel oil, and the addition concentration is 8mg/kg (calculated by iron content). Before the test, the DPF triggers regeneration after the vehicle is expected to travel about 400 km, and the DPF triggers regeneration after the fuel additive containing the ferric oleate is added, so that the DPF actually travels about 2500 km, and the DPF has a certain effect on prolonging the DPF regeneration interval mileage.
It can be seen from examples 1-5 and comparative examples 1-2 that: the fuel additive can effectively reduce the temperature of a balance point, remove carbon deposition of an engine, effectively solve the problem of passive regeneration failure of a DPF particle catcher of a diesel engine, reduce active regeneration times and prolong regeneration mileage, thereby achieving the effects of maintaining the DPF particle catcher, saving oil and reducing maintenance times and cost; in addition, 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, so that the fuel additive disclosed by the invention has good solubility in fuel.
Claims (7)
1. A fuel additive containing crown ether metal complex is characterized in that:
the fuel additive is prepared from components including solvent oil, an amine detergent and a crown ether metal complex;
the components are calculated according to the weight portions,
100 parts by weight of solvent oil;
0.1-30 parts by weight of an amine detergent;
0.01-15 parts by weight of crown ether metal complex;
the boiling range of the solvent oil is 60-200 ℃;
the amine detergent is at least one of polyisobutylene succinimide, polyisobutylene amine and polyether amine;
the crown ether metal complex is prepared from raw materials including crown ether, metal salt, a solvent A and a solvent B; the metal salt is at least one of chloride, nitrate and perchlorate of iron, cerium, platinum and palladium; the solvent A is at least one of chloroform, dichloromethane, dichloroethane and carbon tetrachloride; the solvent B is at least one of acetonitrile, ethanol and water;
the preparation method of the crown ether metal complex comprises the following steps: (1) Dissolving crown ether in a solvent A to prepare crown ether solution; (2) Dissolving metal salt in a solvent B to prepare a salt solution; (3) And mixing the crown ether solution with the salt solution for reaction, and standing for layering or filtering and drying to obtain the crown ether metal complex.
2. The fuel additive of claim 1, wherein:
100 parts by weight of solvent oil;
5-15 parts by weight of an amine detergent;
0.1-5 parts by weight of crown ether metal complex.
3. The fuel additive of claim 1, wherein:
the crown ether is at least one of aza-15-crown ether-5, benzo-15-crown-5-ether, dibenzo-15-crown ether-5, 18-crown-6 ether, benzo-18-crown-6-ether, dibenzo-18-crown ether-6, 21-crown ether-7, benzo-21-crown-7-ether, dibenzo-21-crown 7-ether, 24-crown-8-ether, benzo-24-crown-8-ether, dibenzo-24-crown ether-8 and nitro, amino, hydroxyl, carboxyl and alkylation derivatives thereof.
4. The fuel additive of claim 1, wherein:
an antioxidant can be added into the fuel additive.
5. The fuel additive of claim 4, wherein:
the antioxidant is phenylenediamine, alkyl phenylenediamine, p-tertiary butyl phenol or 2, 6-di-tertiary butyl-p-cresol.
6. A method for preparing the fuel additive according to any one of claims 1 to 5, comprising:
and uniformly mixing the components according to the dosage to obtain the fuel additive containing the crown ether metal complex.
7. Use of a fuel additive according to any one of claims 1 to 5 or prepared by the method of claim 6 for regenerating a diesel particulate trap, characterized in that:
the fuel additive is used by blending with fuel according to the proportion of 1/1000-1/20.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512068A (en) * | 1994-03-02 | 1996-04-30 | Ethyl Corporation | Reducing deposit formation in diesel engines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5512068A (en) * | 1994-03-02 | 1996-04-30 | Ethyl Corporation | Reducing deposit formation in diesel engines |
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