Metal-containing crown ether amine, fuel catalytic regeneration additive and preparation method thereof

Abstract

The application discloses a metal-containing crown ether amine, a fuel catalytic regeneration additive and a preparation method thereof. The metal-containing crown ether amine comprises at least one of compounds containing structures shown in the following formula (1): wherein R is independently selected from methyl or ethyl; R is selected from methyl or ethyl; x1=0-29, x2=0-29, and x1+x2=1-29; R is selected from methyl or ethyl; y1=0-40, y2=0-40, and y1+y2=1-40; m=1-5; n=1-5; and M is a metal ion selected from at least one of potassium, calcium, magnesium, strontium, iron, cobalt, cerium, copper, silver, platinum, palladium, ruthenium and rhodium ions. 1 2 3 4 z+ The fuel catalytic regeneration additive has excellent dispersibility, the crown ether group in the molecular structure of the metal-containing crown ether amine is used as a carrier to complex metal ions such as potassium, calcium, magnesium, iron, cerium, platinum and palladium, and after being added into fuel, the additive is mixed with the fuel for combustion, PM formed in the combustion is closely attached to the surface of a metal catalyst, and the temperature for burning PM can be effectively reduced.​​​​

Description

Technical Field

[0001] This invention relates to the field of fuel catalytic regeneration additives, specifically to a fuel catalytic regeneration additive containing a metal crown ether amine and its preparation method. Background Technology

[0002] The main pollutants emitted by motor vehicle exhaust are carbon monoxide (CO), hydrocarbons (HC), nitrogen oxides (NOx), and particulate matter (PM). Diesel trucks, which account for about 8% of the total number of vehicles, emit 60.0% of NOx and 84.6% of PM. Fuel additives are needed to improve fuel quality, improve engine operation, and reduce pollutant emissions.

[0003] Diesel detergents and fuel catalytic regeneration additives (FBCs) are two important fuel additives for reducing diesel vehicle emissions. Fuel catalytic regeneration additives lower the activation energy of soot particles trapped in the diesel particulate filter (DPF), making it easier to break the chemical bonds between soot particles and achieving DPF regeneration at lower temperatures, thereby reducing emissions. Currently, commercially available fuel catalytic regeneration additives are mainly iron-based and cerium-based organometallic compounds, with organic groups primarily consisting of naphthenic acids, octanoic acid, and oleic acid. These conventional fuel catalytic regeneration additives suffer from drawbacks such as poor dispersibility and limited functionality.

[0004] Therefore, there is an urgent need for a fuel catalytic regeneration additive with good dispersibility and comprehensive functions. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a metal crown ether amine, a fuel catalytic regeneration additive, and a method for preparing the same.

[0006] One object of the present invention is to provide a metal crown ether amine, comprising at least one of compounds containing the structure shown in formula (1) below:

[0007]

[0008] Wherein, R is independently selected from methyl or ethyl; R 1 R 2 Selected from methyl or ethyl; x1 = 0–29, x2 = 0–29, and x1 + x2 = 1–29; R 3 R 4 Selected from methyl or ethyl; y1 = 0–40, y2 = 0–40, and y1 + y2 = 1–40; m = 1–5; n = 1–5; M z+ The metal ion is selected from at least one of potassium, calcium, magnesium, strontium, iron, cobalt, cerium, copper, silver, platinum, palladium, ruthenium, and rhodium ions; Z is selected from 1 to 3; preferably,

[0009] R 1 R 2 Selected from methyl and R 3 R 4 Selected from ethyl, or R 1 R 2 Selected from ethyl and R 3 R 4 Selected from methyl; and / or, x1 = 0–24, x2 = 0–24, and x1 + x2 = 4–24; and / or, y1 = 0–20, y2 = 0–20, and y1 + y2 = 1–20; and / or, m = 1–3; and / or, n = 1–3; and / or, M z+ Selected from at least one of iron, cerium, platinum, palladium, and rhodium ions; more preferably,

[0010] x1 = 0–12, x2 = 0–12, and x1 + x2 = 4–12; and / or y1 = 0–20, y2 = 0–20, and y1 + y2 = 8–20. x1, x2, y1, and y2 represent the average degree of polymerization.

[0011] The structure of the metal crown etheramine in this invention is theoretically calculated based on the chemical reaction mechanism and the amount of added raw materials.

[0012] A second objective of this invention is to provide a method for preparing a metal crown etheramine, which is one of the objectives of this invention, comprising:

[0013] (1) 1,2-propanediol and / or 1,2-butanediol are reacted with propylene oxide or butane oxide in the presence of catalyst A to obtain a polyether intermediate.

[0014] (2) The polyether intermediate obtained in step (1) is reacted with butylene oxide or propylene oxide in the presence of catalyst B to obtain block polyether.

[0015] (3) Dissolve the block polyether and acid-binding agent obtained in step (2) in solvent A and react with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate.

[0016] (4) Dissolve the polyether p-toluenesulfonate obtained in step (3) in solvent B and react it with diaminodibenzo crown ether to obtain crown ether amine;

[0017] (5) Dissolve the crown ether amine obtained in step (4) and the metal salt in solvent C to carry out the reaction to obtain the metal crown ether amine.

[0018] The preferred feature of the metal crown ether amine of the present invention is that it is prepared by the preparation method of the present invention described above.

[0019] In a preferred embodiment of the present invention,

[0020] In step (1),

[0021] The catalyst A is at least one of a DMC bimetallic catalyst and an alkaline catalyst; preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0022] The molar ratio of propylene oxide to 1,2-propanediol or 1,2-butanediol is (1-29):1, preferably (4-24):1, more preferably (4-12):1; and / or, the molar ratio of butylene oxide to 1,2-propanediol or 1,2-butanediol is (1-29):1, preferably (4-24):1, more preferably (4-12):1; and / or,

[0023] The amount of catalyst A is 0.005–2% of the mass of propylene oxide or butane oxide, preferably 0.01–1%; and / or,

[0024] The reaction temperature is 110–140°C, preferably 120–135°C; preferably, the reaction is stopped when the pressure drops to a negative pressure.

[0025] In a preferred embodiment of the present invention,

[0026] In step (2),

[0027] The catalyst B is at least one of a DMC bimetallic catalyst and an alkaline catalyst; preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0028] The molar amount of propylene oxide or butyl oxide is 1 to 40 times that of the polyether intermediate, preferably 1 to 20 times, more preferably 8 to 20 times; and / or,

[0029] The amount of catalyst B is 0.005–2% of the mass of propylene oxide or butane oxide introduced in step (2), preferably 0.01–1%; and / or,

[0030] The reaction temperature is 110–140°C, preferably 120–135°C; preferably, the reaction is stopped when the pressure drops to a negative pressure.

[0031] In a preferred embodiment of the present invention,

[0032] In step (1), propylene oxide is introduced for polymerization, and in step (2), butane oxide is introduced for polymerization; or, in step (1), butane oxide is introduced for polymerization, and in step (2), propylene oxide is introduced for polymerization.

[0033] In a preferred embodiment of the present invention,

[0034] In step (3),

[0035] The acid-binding agent is at least one selected from pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or,

[0036] The amount of the acid-binding agent is 1 to 20 times the molar amount of p-toluenesulfonyl chloride, preferably 1 to 10 times; and / or,

[0037] Solvent A is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0038] The mass of solvent A is 1 to 20 times the mass of the block polyether, preferably 1 to 10 times; and / or,

[0039] The amount of p-toluenesulfonyl chloride used is 2 to 12 times the molar amount of the block polyether, preferably 2 to 10 times, more preferably 2 to 5 times; and / or,

[0040] The reaction temperature with p-toluenesulfonyl chloride is 0–40°C, preferably 5–20°C; and / or the reaction time with p-toluenesulfonyl chloride is 6–72 h, preferably 18–48 h.

[0041] In a preferred embodiment of the present invention,

[0042] In step (4),

[0043] The structure of the diaminodibenzocrown ether is as follows:

[0044] Wherein, m = 1–5, n = 1–5; preferably, the diaminodibenzo-12-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, diaminodibenzo-21-crown-7 ether, and diaminodibenzo-24-crown-8 ether; and / or,

[0045] Solvent B is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or,

[0046] The mass of solvent B is 1 to 20 times the mass of polyether p-toluenesulfonate, preferably 1 to 10 times; and / or,

[0047] The amount of the diaminodibenzocrown ether is 2 to 6 times, preferably 2 to 4 times, the molar amount of the polyether p-toluenesulfonate; and / or,

[0048] The reaction temperature is 40–160°C, preferably 80–140°C; and / or the reaction time is 12–90 h, preferably 18–60 h.

[0049] In a preferred embodiment of the present invention,

[0050] In step (5),

[0051] The metal salt is at least one of the following: chloride, nitrate, acetate, and perchlorate of potassium, calcium, magnesium, strontium, iron, cobalt, cerium, copper, silver, platinum, palladium, ruthenium, and rhodium; preferably at least one of the following: chloride, nitrate, acetate, and perchlorate of iron, cerium, platinum, palladium, and rhodium; and / or,

[0052] The solvent C is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, acetonitrile, ethanol, methanol, N,N-dimethylformamide, and N,N-dimethylacetamide; and / or,

[0053] The amount of solvent C used is 0.5 to 20 times the mass of the metal salt, preferably 1 to 10 times; and / or,

[0054] The molar amount of metal ions in the metal salt is 2 to 20 times that of crown ether amine, preferably 2 to 10 times; and / or,

[0055] The reaction temperature is 40–200°C, preferably 100–160°C, and / or the reaction time is 2–24 h, preferably 10–20 h.

[0056] The preparation method of the metal crown ether amine of the present invention can adopt the following specific technical solutions:

[0057] (1) The initiator 1,2-propanediol or 1,2-butanediol and DMC bimetallic catalyst are put into a high-pressure reactor, the air is removed by vacuuming, and then the temperature is raised to 110-140°C. Propylene oxide or epoxide with a molar ratio of (1-29):1 to the initiator 1,2-propanediol or 1,2-butanediol is introduced to carry out the polymerization reaction. The reaction pressure is controlled not to exceed 0.3 MPa. After the reaction is completed, the temperature is maintained and the reaction is continued. After the pressure drops to negative pressure, the temperature is lowered to below 80°C and the reaction product is taken out to obtain the polyether intermediate.

[0058] (2) The polyether intermediate and DMC bimetallic catalyst obtained in step (1) are put into a high-pressure reactor, the air is removed by vacuuming, and then the temperature is raised to 110-140°C. Butane oxide or propylene oxide with a total molar amount of 1-40 times that of the polyether intermediate is introduced to carry out the polymerization reaction. The reaction pressure is controlled not to exceed 0.3 MPa. After the reaction is completed, the temperature is kept high. After the pressure drops to negative pressure, the temperature is lowered to below 80°C and the reaction product is taken out to obtain block polyether.

[0059] (3) Add the block polyether, acid-binding agent, p-toluenesulfonyl chloride and solvent A obtained in step (2) to the reaction vessel and stir the reaction at 0-40℃ for 6-72h. After the reaction is completed, pour it into a beaker, add deionized water to wash the reaction solution, separate the solution with a separatory funnel, and after washing with water, rotary evaporate the reaction solution to obtain polyether p-toluenesulfonate.

[0060] (4) Add diaminodibenzocrown ether and solvent B to the reaction vessel, stir evenly and heat to 40-160℃; dissolve the polyether p-toluenesulfonate obtained in step (3) in solvent B, and slowly drop it into the diaminodibenzocrown ether solution through a constant pressure dropping funnel, so that the polyether p-toluenesulfonate reacts with diaminodibenzocrown ether for 12-90h. After the reaction is completed, wash with water and evaporate the solvent to obtain crown ether amine.

[0061] (5) Take metal salt (based on the number of moles of metal ions) and crown ether amine (based on the number of moles of crown ether) in a molar ratio of 1 to 10:1. Mix and dissolve crown ether amine and metal salt in solvent C. React at 40 to 200°C for 2 to 24 hours. After the reaction is complete, add water and solvent D for extraction. Evaporate the solvent from the organic phase to obtain metal crown ether amine.

[0062] In a preferred embodiment of the present invention,

[0063] The solvent D is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, and toluene; and / or,

[0064] The mass of solvent D is 0.5 to 20 times the mass of the metal salt, preferably 1 to 10 times.

[0065] A third objective of this invention is to provide a fuel catalytic regeneration additive, comprising the following components:

[0066] 1) Solvent oil; 2) Metal crown ether amines prepared by one of the purposes of this invention or by another method of this invention; 3) Acetylene glycol polyether; 4) Optional antioxidant.

[0067] In a preferred embodiment of the present invention,

[0068] The solvent oil is a conventional solvent oil in the art, preferably an alkane solvent oil or an aromatic solvent oil with a boiling range of 60–200°C, or a C6–C4 solvent oil. 12 At least one of alkyl alcohols, more preferably at least one of 60# solvent oil, 80# solvent oil, and 100# solvent oil; and / or,

[0069] The structural formula of the acetylenic diol polyether is as follows:

[0070]

[0071] Wherein, R2 and R3 are methyl groups, R1 and R4 may be the same or different, and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 may be the same or different, m1+m2 = 0 to 16, n1 and n2 may be the same or different, n1+n2 = 0 to 20, and m1, m2, n1, and n2 are not simultaneously 0; (the acetylenic diol polyether is preferably prepared by the method in Chinese Patent 202211702264.2, which is incorporated herein by reference in its entirety) and / or,

[0072] The antioxidant is a conventional antioxidant in the art, preferably at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, and 4,4-butylene-bis(3-methyl-6-tert-butylphenol).

[0073] In a preferred embodiment of the present invention,

[0074] Each component is based on 100 parts by weight of solvent oil.

[0075] It contains 10 to 100 parts by weight of a metal crown ether amine; preferably 20 to 80 parts by weight; more preferably 30 to 60 parts by weight.

[0076] 0.5 to 10 parts by weight of acetylacetonate diol polyether; preferably 1 to 8 parts by weight; more preferably 1 to 5 parts by weight;

[0077] Antioxidant 0-2 parts by weight; preferably 0.5-2 parts by weight.

[0078] The formulation of the fuel catalytic regeneration additive of the present invention may also include conventional components in the art, such as polyether, and the dosage is also conventional. Technicians can adjust it according to the actual situation.

[0079] The fourth objective of this invention is to provide a method for preparing a fuel catalytic regeneration additive as described in the third objective of this invention, comprising uniformly mixing components including the metal crown ether amine, solvent oil, acetylsene glycol polyether, and optionally an antioxidant to obtain the fuel catalytic regeneration additive.

[0080] Compared with existing technologies, the present invention has the following beneficial effects: The fuel catalytic regeneration additive of the present invention has excellent dispersibility. The crown ether group in the metal crown ether amine molecular structure acts as a carrier to complex metal ions such as potassium, calcium, magnesium, iron, cerium, platinum, and palladium. After being added to fuel, it mixes and burns with the fuel, and the resulting particulate matter (PM) adheres tightly to the surface of the metal catalyst, reducing the combustion temperature of the PM. The fuel catalytic regeneration additive of the present invention not only has good dispersibility and reduces the amount of carbon deposits in vehicle engines, but also effectively lowers the equilibrium point temperature, solving the problem of passive regeneration failure of diesel engine particulate filters (DPFs), reducing the number of active regeneration cycles, and extending the regeneration mileage. Detailed Implementation

[0081] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0082] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0083] Preparation of decantyne diol polyoxypropylene (4) ether in Example 1:

[0084] (1) Preparation of nanocatalysts (Mg / Al / Co composite metal oxide catalysts):

[0085] Prepare a mixed solution I of NaOH and Na₂CO₃ with a molar ratio of 2:1 (100 mL, where the molar concentration of Na₂CO₃ is 0.5 mol / L). Prepare a mixed solution II of Mg(NO₃)₂ and Al(NO₃)₃ with a molar ratio of 3:1 (100 mL, where the molar concentration of Al(NO₃)₃ is 0.5 mol / L). Prepare an equal volume of CoNO₃ solution to the concentration of mixed solution II. The concentration of Al(NO3)3 was 1 / 5; the CoNO3 solution was kept at 60℃ and mixed solution I and mixed solution II were added dropwise simultaneously with vigorous stirring, and the pH value was controlled at 8.5-9.5 during the dropwise addition; after the dropwise addition was completed, the reaction solution was stirred at a constant temperature for 30 min, and then placed in an oven at 100℃ for crystallization for 12 hours; the crystallized slurry was filtered and washed until the filtrate was neutral, and the filter cake was placed in an oven to dry; the dried solid was ball-milled to obtain the Mg / Al / Co composite metal oxide catalyst.

[0086] (2) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10, the structural formula of tetramethyldecynediol is: Wherein, R2 and R3 are -CH3, and R1 and R4 are both -CH2CH(CH3)2) and 0.9g of the Mg / Al / Co composite metal oxide catalyst obtained in step (1) above are added to a high-pressure reactor, stirred evenly, and the air in the reactor is replaced with nitrogen three times. The high-pressure reactor is evacuated at 80°C for 30 minutes using a vacuum pump, and then the evacuation is stopped. 0.8mol of propylene oxide is slowly introduced into the reactor through the feed pipe, and the reactor temperature is raised to 115°C. The pressure in the reactor is controlled at about 0.20MPa, and the reaction is stirred for 4 hours. After the pressure in the reactor drops to negative pressure, the reaction is stopped, the reaction mixture is taken out, and the nano-catalyst is removed by microporous membrane filtration to obtain decynyl diol polyoxypropylene (4) ether (TMAD10-PO4). The structural formula of the above decynyl diol polyoxypropylene (4) ether (TMAD10-PO4) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=0, n1+n2=4.

[0087] Preparation of decantyne diol polyoxyethylene (8) polyoxypropylene (4) ether in Examples 2 and 3:

[0088] (1) 0.2 mol of tetramethyldecynyl diol (TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were added to a high-pressure reactor and stirred evenly. The air inside the reactor was replaced with nitrogen three times. The reactor was then evacuated at 80°C for 30 min using a vacuum pump. The evacuation was then stopped. 1.6 mol of ethylene oxide was slowly introduced into the reactor through the feed pipe, and the reactor temperature was raised to 115°C. The pressure inside the reactor was controlled at around 0.20 MPa, and the reaction was stirred for 4 h. The reaction was stopped after the pressure inside the reactor dropped to negative pressure. The reaction mixture was removed, and the nano-catalyst was removed by microporous membrane filtration to obtain decynyl diol polyoxyethylene ether (TMAD10-EO8). The structural formula of the above decynyl diol polyoxyethylene ether (TMAD10-EO8) is as follows: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=0;

[0089] (2) 0.1 mol TMAD10-EO8 and 0.8 g Mg / Al / Co composite metal oxide catalyst were added to a high-pressure reactor and stirred evenly. The air inside the reactor was replaced with nitrogen three times. The reactor was evacuated at 80°C for 30 min using a vacuum pump. The evacuation was then stopped. 0.4 mol propylene oxide was introduced into the reactor through the feed pipe, and the reactor temperature was raised to 125°C. The pressure inside the reactor was controlled at about 0.3 MPa. The reactor was stirred for 12 h. The reaction was stopped after the pressure inside the reactor dropped to negative pressure. The reaction mixture was removed and the nano-catalyst was removed by microporous membrane filtration to obtain decynyl diol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4). The structural formula of the above decynyl diol polyoxyethylene polyoxypropylene ether (TMAD10-EO8-PO4) is as follows: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=4.

[0090] The structure of the acetylenic diol polyether obtained above was theoretically calculated based on the reaction mechanism and the added raw materials.

[0091] Example 1

[0092] Preparation of metal crown etheramines:

[0093] (1) 90g (1mol) of 1,2-butanediol and 0.072g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 135℃. 720g (10mol) of epoxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80℃ and the reaction product was taken out to obtain polyoxybutene (11) ether intermediate.

[0094] (2) 1 mol of the above polyoxybutene (11) ether intermediate and 0.29 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 130°C. 580 g (10 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (11) polyoxypropylene (10) ether.

[0095] (3) 1 mol of polyoxybutene (11) polyoxypropylene (10) ether, 618 g (3.2 mol) of p-toluenesulfonyl chloride, and 632 g (8 mol) of pyridine were dissolved in 2000 g of dichloromethane and stirred at 10 °C for 24 h. After the reaction was completed, the mixture was poured into a beaker and deionized water was added to wash the reaction solution. The mixture was separated by a separatory funnel and the solvent was removed by rotary evaporation after three water washes to obtain polyoxybutene (11) polyoxypropylene (10) ether p-toluenesulfonate.

[0096] (4) Add 2 mol of diaminodibenzo-21-crown 7 ether (CAS: 317854-59-4) and 872 g of toluene to the reaction vessel, stir evenly and heat to 120℃; dissolve 1 mol of polyoxybutene (11) polyoxypropylene (10) ether p-toluenesulfonate obtained in step (3) in 2000 g of toluene, and slowly drop it into the diaminodibenzo-21-crown 7 ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 24 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxybutene (11) polyoxypropylene (10) ether bis-diaminodibenzo-21-crown 7 ether amine;

[0097] (5) Add 388g (2mol) of ferric acetate, 0.5mol of polyoxybutene (11)polyoxypropylene (10) ether bis-diaminodibenzo-21-crown 7-etheramine and 3000g of N,N-dimethylformamide to the reaction vessel, heat to 150℃, react for 12 hours with stirring, stop the reaction, cool to room temperature, add water and dichloroethane for extraction, and after the solvent is removed from the organic phase, polyoxybutene (11)polyoxypropylene (10) ether bis-diaminodibenzo-21-crown 7-etheramine-iron complex is obtained, which is simply referred to as metal crown ether etheramine (Fe-21C7-PEA).

[0098] Preparation of fuel catalytic regeneration additives:

[0099] Mix 100 parts by weight of 60# solvent oil, 30 parts by weight of metal crown ether amine (Fe-21C7-PEA), 2.5 parts by weight of decynyl diol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine at 50°C to obtain fuel catalytic regeneration additive i#.

[0100] Example 2

[0101] Preparation of metal crown etheramines:

[0102] (1) 90g (1mol) of 1,2-butanediol and 0.36g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 125°C. 360g (5mol) of epoxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) ether intermediate.

[0103] (2) 1 mol of the above polyoxybutene (6) ether intermediate and 0.23 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 130°C. 1160 g (20 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high and the reaction was continued. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) polyoxypropylene (20) ether.

[0104] (3) Dissolve 1 mol of polyoxybutene (6) polyoxypropylene (20) ether, 927 g of p-toluenesulfonyl chloride, and 948 g of pyridine in 4000 g of dichloroethane and stir at 20 °C for 24 h. After the reaction is completed, pour the solution into a beaker and add deionized water to wash the reaction solution. Separate the solution with a separatory funnel and remove the solvent by rotary evaporation after three water washes to obtain polyoxybutene (6) polyoxypropylene (20) ether p-toluenesulfonate.

[0105] (4) Add 4 mol of diaminodibenzo-18-crown 6 ether (CAS: 31406-52-7) and 1568 g of xylene to the reaction vessel, stir evenly and heat to 100℃; dissolve 1 mol of polyoxybutene (6) polyoxypropylene (20) ether p-toluenesulfonate obtained in step (3) in 2000 g of xylene, and slowly drop it into the diaminodibenzo-18-crown 6 ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 48 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxybutene (6) polyoxypropylene (20) ether bis-diaminodibenzo-18-crown 6 ether amine.

[0106] (5) Add 952g (3mol) of cerium acetate, 0.5mol of polyoxybutene (6) polyoxypropylene (20) ether bis-diaminodibenzo-18 crown 6 etheramine and 3000g of N,N-dimethylacetamide to the reaction vessel, heat to 150℃, react for 18 hours with stirring, stop the reaction, cool to room temperature, add water and dichloromethane for extraction, and after the solvent is removed from the organic phase, polyoxybutene (6) polyoxypropylene (20) ether bis-diaminodibenzo-18 crown 6 etheramine-cerium complex is obtained, which is simply referred to as metal crown ether etheramine (Ce-18C6-PEA).

[0107] Preparation of fuel catalytic regeneration additives:

[0108] Mix 100 parts by weight of 80# solvent oil, 30 parts by weight of metal crown ether amine (Ce-18C6-PEA), 4 parts by weight of decynyl glycol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel catalytic regeneration additive ii#.

[0109] Example 3

[0110] Preparation of metal crown etheramines:

[0111] (1) 76g (1mol) of 1,2-propanediol and 0.12g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 130°C. 522g (9mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxypropylene (10) ether intermediate.

[0112] (2) 1 mol of the above polyoxypropylene (10) ether intermediate and 0.43 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 135°C. 1080 g (15 mol) of epoxy butane was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxypropylene (10) polyoxybutene (15) ether.

[0113] (3) Dissolve 1 mol of polyoxypropylene (10) polyoxybutene (15) ether, 773 g of p-toluenesulfonyl chloride, and 790 g of pyridine in 4000 g of dichloroethane and stir at 5 °C for 48 h. After the reaction is completed, pour the solution into a beaker and add deionized water to wash the reaction solution. Separate the solution with a separatory funnel and remove the solvent by rotary evaporation after three water washes to obtain polyoxypropylene (10) polyoxybutene (15) ether p-toluenesulfonate.

[0114] (4) Add 4 mol of diaminodibenzo-15-crown 5-ether (CAS: 313496-30-9) and 1392 g of ethylbenzene to the reaction vessel, stir evenly and heat to 110℃; dissolve 1 mol of polyoxypropylene (10) polyoxybutene (15) ether p-toluenesulfonate obtained in step (3) in 2000 g of ethylbenzene, and slowly drop it into the diaminodibenzo-15-crown 5-ether solution through a constant pressure dropping funnel (at a rate of 1 mL / min), react for 48 h, wash with water after the reaction is completed, evaporate the solvent, and obtain polyoxypropylene (10) polyoxybutene (15) ether bis-diaminodibenzo-15-crown 5-ether amine.

[0115] (5) Add 460g (2mol) of palladium nitrate, 0.5mol of polyoxypropylene (10) polyoxybutene (15) ether bis-diaminodibenzo-15 crown 5 etheramine and 3000g of N,N-dimethylacetamide to the reaction vessel, heat to 120℃, react for 18 hours with stirring, stop the reaction, cool to room temperature, add water and chloroform for extraction, and after the solvent is removed from the organic phase, the polyoxypropylene (10) polyoxybutene (15) ether bis-diaminodibenzo-15 crown 5 etheramine-palladium complex is obtained, which is simply referred to as metal crown ether amine (Pd-15C5-PEA).

[0116] Preparation of fuel catalytic regeneration additives:

[0117] Mix 100 parts by weight of 100# solvent oil, 50 parts by weight of metal crown ether amine (Pd-15C5-PEA), 1 part by weight of decynyl glycol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel catalytic regeneration additive iii#.

[0118] Comparative Example 1

[0119] Preparation of polyoxybutene-polyoxypropylene etheramine:

[0120] (1) 90g (1mol) of 1,2-butanediol and 0.36g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 125°C. 360g (5mol) of epoxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the temperature was kept high. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) ether intermediate.

[0121] (2) 1 mol of the above polyoxybutene (6) ether intermediate and 0.23 g of DMC bimetallic catalyst (Huaian Bader Polyurethane Technology Co., Ltd.) were put into a high-pressure reactor, the air was removed by vacuuming, and then the reactor was heated to 130°C. 1160 g (20 mol) of propylene oxide was introduced to carry out the polymerization reaction. The reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the temperature was kept high and the reaction was continued. After the pressure dropped to negative pressure, the temperature was lowered to 80°C and the reaction product was taken out to obtain polyoxybutene (6) polyoxypropylene (20) ether.

[0122] (3) 500g of polyoxybutene (6)polyoxypropylene (20) ether and 50g of Raney nickel catalyst (CAS No. 7440-02-0) were put into a reaction vessel, the air inside the vessel was removed by vacuuming, 90g of liquid ammonia and 6mol of hydrogen were introduced, and the amination reaction was carried out at 9MPa and 190℃ for 8h. Then the mixture was cooled to 80℃, the mixture obtained from the reaction was taken out, the insoluble matter was removed by filtration, and the unreacted liquid ammonia was removed by evaporation of the filtrate to obtain polyoxybutene (6)polyoxypropylene (20) ether amine.

[0123] Preparation of metal crown ethers:

[0124] 952 g (3 mol) of cerium acetate, 1 mol of diaminodibenzo-18-crown-6 ether, and 3000 g of N,N-dimethylacetamide were added to a reaction vessel. The temperature was raised to 150 °C, and the reaction was carried out for 18 hours with stirring. The reaction was then stopped, cooled to room temperature, and extracted with water and dichloromethane. After the solvent was removed from the organic phase by evaporation, diaminodibenzo-18-crown-6 ether-cerium complex was obtained, which is simply referred to as metal crown ether (Ce-18C6).

[0125] Preparation of fuel catalytic regeneration additives:

[0126] Mix 100 parts by weight of 80# solvent oil, 12 parts by weight of metal crown ether (Ce-18C6), 18 parts by weight of polyoxybutene (6), polyoxypropylene (20) ether amine, 4 parts by weight of decynyl glycol polyoxyethylene (8), polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel catalytic regeneration additive iv#.

[0127] Comparative Example 2

[0128] Preparation of fuel catalytic regeneration additives:

[0129] Mix 100 parts by weight of 80# solvent oil, 30 parts by weight of polyisobutylene succinimide, 4 parts by weight of decynyl glycol polyoxyethylene (8) polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel catalytic regeneration additive v#.

[0130] Comparative Example 3

[0131] Preparation of fuel catalytic regeneration additives:

[0132] 100 parts by weight of 80# solvent oil, 30 parts by weight of polyoxybutylene (6), polyoxypropylene (20), etheramine prepared in Comparative Example 1, 4 parts by weight of decynyl glycol polyoxyethylene (8), polyoxypropylene (4) ether (same as in Example 2), and 0.5 parts by weight of p-tert-butylphenol were mixed evenly at 50°C to obtain fuel catalytic regeneration additive vi#.

[0133] Test Example 1

[0134] The low-temperature dispersion performance of fuel catalytic regeneration additives was tested using the sludge spot dispersion test method. The sludge spot dispersion value (SDD) was used to evaluate the low-temperature dispersion performance of the fuel catalytic regeneration additives; the higher the SDT value, the better the sludge dispersion performance of the fuel catalytic regeneration additives at low temperatures. The sludge dispersibility test was conducted according to the SH / T 0623-95 procedure. Without the addition of fuel catalytic regeneration additives, the STD value was 20. After adding 10 wt.% of the fuel catalytic regeneration additives, the STD value was retested, and the results are listed in Table 1.

[0135] The nozzle coking test was conducted according to the methods and technical requirements specified in SH / T 0764 "Test Method for Coking of Diesel Engine Nozzles (XUD-9 Method)". The average air flow loss of cylinders 1-4 with a needle valve lift of 0.1 mm was 85.5% when no fuel catalytic regeneration additive was added. The air flow loss of cylinders 1-4 with a needle valve lift of 0.1 mm was tested when fuel catalytic regeneration additive was added at a volume ratio of 1:1000 to diesel. The results are listed in Table 1.

[0136] Bench tests were conducted using a Weichai WP13 heavy-duty diesel engine. The bench test setup included the diesel engine, dynamometer, aftertreatment system including DOC, DPF (DPF) and SCR, and data acquisition system. The exhaust temperature was adjusted by regulating the engine's operating point, and the DPF deposit equilibrium point temperature was measured, starting at 300℃ and increasing by 20℃ each time, ending at 440℃. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference across the DPF. For the same aftertreatment unit (DPF including catalyst coating), the equilibrium point temperature was 400℃ before adding fuel catalytic regeneration additive. The fuel catalytic regeneration additive was added to the diesel fuel at a volume ratio of 1:100, and the equilibrium point temperature was tested. The results are listed in Table 1.

[0137] A small truck equipped with a 2.0L CTI diesel engine was used for a real-vehicle test. The truck's DPF volume was 3.3L, with a rated maximum carbon load of 20g, and the vehicle's regeneration interval mileage was approximately 500km. During the test, a fuel catalytic regeneration additive was added to the diesel fuel at a concentration of 10mg / kg (based on metal ion content). Before the test, the vehicle was expected to travel approximately 400km before the DPF would trigger regeneration. The actual mileage results after adding the fuel catalytic regeneration additive are listed in Table 1.

[0138] Table 1. Performance comparison of fuel additives in the examples and comparative examples.

[0139]

[0140] As can be seen from Examples 2, Comparative Examples 1 and 3, and Table 1, compared with the addition of polyetheramine (Comparative Example 3) prepared under the same conditions of the present invention using conventional initiators (such as propylene glycol or butanediol) in the fuel catalytic regeneration additive, or the further addition of metal crown ether (Comparative Example 1), the fuel catalytic regeneration additive containing metal crown ether amine of the present invention has significantly better dispersibility and can more effectively reduce the equilibrium point temperature, solve the problem of passive regeneration failure of diesel engine particulate filter (DPF), reduce the number of active regenerations, and extend the regeneration mileage.

[0141] As can be seen from Examples 1-3 and Table 1, the fuel catalytic regeneration additive of the present invention, when added to fuel, not only has good dispersibility and reduces the amount of carbon deposits in vehicle engines, but also effectively lowers the equilibrium point temperature, solves the problem of passive regeneration failure of diesel engine particulate filters (DPF), reduces the number of active regeneration cycles, and extends the regeneration mileage.

Claims

1. A metal crown ether amine, comprising at least one of compounds containing the structure shown in formula (1): Equation (1) in, R is independently selected from methyl or ethyl; R 1 R 2 Selected from methyl or ethyl; x1 = 0~29, x2 = 0~29, and x1 + x2 = 1~29; R 3 R 4 Selected from methyl or ethyl; y1=0~40, y2=0~40, and y1+y2=1~40; m=1~5; n=1~5; M z+ It is a metal ion, selected from at least one of potassium, calcium, magnesium, strontium, iron, cobalt, cerium, copper, silver, platinum, palladium, ruthenium, and rhodium ions.

2. The metal crown-containing ether amine according to claim 1, characterized in that: R 1 R 2 Selected from methyl and R 3 R 4 Selected from ethyl, or R 1 R 2 Selected from ethyl and R 3 R 4 Selected from methyl; and / or, x1 = 0~24, x2 = 0~24, and x1 + x2 = 4~24; and / or, y1 = 0~20, y2 = 0~20, and y1 + y2 = 1~20; and / or, m = 1~3; and / or, n = 1~3; and / or, M z+ It is selected from at least one of the following: iron, cerium, platinum, palladium, and rhodium ions.

3. A method for preparing a metal crown ether amine as described in claim 1 or 2, comprising: (1) 1,2-propanediol and / or 1,2-butanediol are reacted with propylene oxide or butane oxide in the presence of catalyst A to obtain a polyether intermediate. (2) The polyether intermediate obtained in step (1) is reacted with butane or propylene oxide in the presence of catalyst B to obtain block polyether. (3) Dissolve the block polyether and acid-binding agent obtained in step (2) in solvent A and react with p-toluenesulfonyl chloride to obtain polyether p-toluenesulfonate; (4) Dissolve the polyether p-toluenesulfonate obtained in step (3) in solvent B and react it with diaminodibenzocrown ether to obtain crown ether amine; (5) Dissolve the crown ether amine obtained in step (4) and the metal salt in solvent C to carry out the reaction to obtain the metal crown ether amine.

4. The preparation method according to claim 3, characterized in that: In step (1), The catalyst A is at least one of a DMC bimetallic catalyst and an alkaline catalyst; and / or... The molar ratio of propylene oxide to 1,2-propanediol or 1,2-butanediol is (1~29):1; and / or, the molar ratio of butylene oxide to 1,2-propanediol or 1,2-butanediol is (1~29):1; and / or, The amount of catalyst A is 0.005~2% of the mass of propylene oxide or butane oxide; and / or, The reaction temperature is 110~140℃; and / or, In step (2), The catalyst B is at least one of a DMC bimetallic catalyst and an alkaline catalyst; and / or The molar amount of propylene oxide or butyl oxide is 1 to 40 times the molar amount of the polyether intermediate; and / or, The amount of catalyst B is 0.005~2% of the mass of propylene oxide or butane oxide introduced in step (2); and / or, The reaction temperature is 110~140℃.

5. The preparation method according to claim 4, characterized in that: In step (1), The alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or, The molar ratio of propylene oxide to 1,2-propanediol or 1,2-butanediol is (4~24):1; and / or, the molar ratio of butylene oxide to 1,2-propanediol or 1,2-butanediol is (4~24):1; and / or, The amount of catalyst A is 0.01~1% of the mass of propylene oxide or butane oxide; and / or, The reaction temperature is 120~135℃; and / or, In step (2), The alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, sodium ethoxide, and sodium hydride; and / or, The molar amount of propylene oxide or butyl oxide is 1 to 20 times the molar amount of the polyether intermediate; and / or, The amount of catalyst B is 0.01~1% of the mass of propylene oxide or butane oxide introduced in step (2); and / or, The reaction temperature is 120~135℃.

6. The preparation method according to claim 3, characterized in that: In step (3), The acid-binding agent is at least one selected from pyridine, triethylamine, diisopropylethylamine, sodium acetate, sodium carbonate, and potassium carbonate; and / or, The amount of the acid-binding agent is 1 to 20 times the molar amount of p-toluenesulfonyl chloride; and / or, Solvent A is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The mass of solvent A is 1 to 20 times the mass of the block polyether; and / or, The amount of p-toluenesulfonyl chloride used is 2 to 12 times the molar amount of the block polyether; and / or, The reaction temperature with p-toluenesulfonyl chloride is 0~40℃; and / or the reaction time with p-toluenesulfonyl chloride is 6~72 h.

7. The preparation method according to claim 6, characterized in that: In step (3), The amount of the acid-binding agent is 1 to 10 times the molar amount of p-toluenesulfonyl chloride; and / or, The mass of solvent A is 1 to 10 times the mass of the block polyether; and / or, The amount of p-toluenesulfonyl chloride used is 2 to 10 times the molar amount of the block polyether; and / or, The reaction temperature with p-toluenesulfonyl chloride is 5~20℃; and / or the reaction time with p-toluenesulfonyl chloride is 18~48 h.

8. The preparation method according to claim 3, characterized in that: In step (4), The structure of the diaminodibenzocrown ether is as follows: Where m = 1~5, n = 1~5; and / or, Solvent B is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, trimethylbenzene, and ethylbenzene; and / or, The mass of solvent B is 1 to 20 times the mass of polyether p-toluenesulfonate; and / or, The amount of the diaminodibenzocrown ether is 2 to 6 times the molar amount of the polyether p-toluenesulfonate; and / or, The reaction temperature is 40~160℃; and / or the reaction time is 12~90 h.

9. The preparation method according to claim 8, characterized in that: In step (4), The diaminodibenzo-crown ether is at least one selected from diaminodibenzo-12-crown-4 ether, diaminodibenzo-15-crown-5 ether, diaminodibenzo-18-crown-6 ether, diaminodibenzo-21-crown-7 ether, and diaminodibenzo-24-crown-8 ether; and / or The mass of solvent B is 1 to 10 times the mass of polyether p-toluenesulfonate; and / or, The amount of the diaminodibenzocrown ether is 2 to 4 times the molar amount of the polyether p-toluenesulfonate; and / or, The reaction temperature is 80~140℃; and / or the reaction time is 18~60 h.

10. The preparation method according to claim 3, characterized in that: In step (5), The metal salt is at least one of the following: chloride, nitrate, acetate, or perchlorate of potassium, calcium, magnesium, strontium, iron, cobalt, cerium, copper, silver, platinum, palladium, ruthenium, and rhodium; and / or, The solvent C is at least one selected from dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, acetonitrile, ethanol, methanol, N,N-dimethylformamide, and N,N-dimethylacetamide; and / or, The amount of solvent C used is 0.5 to 20 times the mass of the metal salt; and / or, The molar amount of metal ions in the metal salt is 2 to 20 times that of crown ether amine; and / or, The reaction temperature is 40~200℃, and / or the reaction time is 2~24h.

11. The preparation method according to claim 10, characterized in that: In step (5), The metal salt is at least one of the following: chloride, nitrate, acetate, and perchlorate of iron, cerium, platinum, palladium, and rhodium; and / or, The amount of solvent C used is 1 to 10 times the mass of the metal salt; and / or, The molar amount of metal ions in the metal salt is 2 to 10 times that of crown ether amine; and / or, The reaction temperature is 100~160℃, and / or the reaction time is 10~20h.

12. A fuel catalytic regeneration additive, comprising the following components: 1) Solvent oil; 2) Metal crown ether amine as described in claim 1 or 2 or metal crown ether amine obtained by any of the preparation methods described in claims 3-11; 3) Acetylene glycol polyether; 4) Optional antioxidant.

13. The fuel catalytic regeneration additive as described in claim 12, characterized in that: The solvent oil is an alkane solvent oil with a boiling range of 60~200℃, an aromatic solvent oil with a boiling range of 60~200℃, or a C6~C4 solvent oil. 12 At least one of alkyl alcohols; and / or, The structural formula of the acetylenic diol polyether is as follows: Wherein, R2 and R3 are methyl groups; R1 and R4 may be the same or different, and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 may be the same or different, with m1 + m2 = 0 to 16; n1 and n2 may be the same or different, with n1 + n2 = 0 to 20; and m1, m2, n1, and n2 are not simultaneously 0; and / or, The antioxidant is phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6 Second Uncle Ding Ji 4 Ethylphenol, 4,4 Iodine-Bis(3) methyl 6 At least one of tert-butylphenol.

14. The fuel catalytic regeneration additive as described in claim 12 or 13, characterized in that: Each component is based on 100 parts by weight of solvent oil. Contains 10-100 parts by weight of metal crown ether amine; 0.5-10 parts by weight of acetylacetonate diol polyether; Antioxidant 0-2 parts by weight.

15. The fuel catalytic regeneration additive as described in claim 14, characterized in that: Each component is based on 100 parts by weight of solvent oil. Contains 20-80 parts by weight of metal crown ether amine; 1-8 parts by weight of acetylacetonate diol polyether; Antioxidant 0.5 to 2 parts by weight.

16. A method for preparing a fuel catalytic regeneration additive as described in any one of claims 12-15, comprising uniformly mixing a component comprising the metal crown ether amine, solvent oil, acetylacetonate diol polyether, and optionally an antioxidant to obtain the fuel catalytic regeneration additive.

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