A quaternary ammonium mannich base, a quaternary ammonium mannich base multifunctional fuel additive and a preparation method and application thereof

Abstract

The application discloses a kind of quaternary ammonium mannich base, quaternary ammonium mannich base multifunctional fuel additive and its preparation method and application.The quaternary ammonium mannich base, its structural formula is as shown below:Wherein, m=10~90, preferably m=15~80;N=0~20, preferably n=2~10;R1, R2, R3 same or not same, respectively independently H or C1-C4 alkyl;R4 is H, CH3 Or C2H5;R5 is C3-C8 alkyl or aryl, preferably C3-C8 alkyl;R6 is CH3 Or C2H5;X is SO4 Or CO3.The multifunctional fuel additive comprising quaternary ammonium mannich base of the application not only has good dispersibility, has the effect of reducing the accumulation amount of vehicle engine carbon deposit, but also can effectively reduce the balance point temperature, solve diesel engine particulate filter (DPF) passive regeneration failure, reduce the number of active regeneration, prolong regeneration mileage.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fuel additives, in particular to a quaternary ammonium Mannich base, a quaternary ammonium Mannich base multifunctional fuel additive and a preparation method and application thereof. BACKGROUND

[0002] According to the data released by the ecological environment department, automobiles are the main contributors to motor vehicle air pollution emissions, and more than 90% of CO, NOx and PM and more than 80% of HC are emitted. Diesel trucks, which account for 7.9% of the total number of automobiles, emit 60.0% of NOx and 84.6% of PM, and are the top priority of motor vehicle pollution prevention and control. With the release and implementation of the national VI emission regulations, the standards for automobile exhaust emissions in China are becoming more and more stringent. In addition to improving oil refining technology, using fuel additives has become one of the important technical means to improve fuel quality and improve engine operating conditions.

[0003] Fuel additive is a kind of additive for improving the performance of fuel, including antiknock agent, antioxidant, metal passivator, anti-icing agent, antistatic additive, anti-wear agent, low temperature fluidity improver, cetane number improver, detergent, combustion improver, fuel borne catalyst regeneration additive (FBC) and so on. The existing diesel additive on the market has single function, and there are few multi-effect composite additives, which are mainly used to improve the combustion performance and detergency of diesel, and the effect is not obvious in reducing the emission of diesel vehicle pollutants. Diesel detergent is mainly based on dispersant, which is a high-efficiency surfactant. Its polar group has strong adsorption capacity to the formed carbon deposit and sediment, which can make the carbon deposit and sediment gradually loose and become small particles washed down, and at the same time, the dispersant can prevent small particles from forming large particles and gathering on the metal surface, playing a cleaning role and protecting the normal operation of the engine. Diesel detergent can be divided into two categories according to whether it contains metal components: ash-containing diesel detergent and ash-free diesel detergent. Ash-containing detergent has excellent combustion and smoke suppression effect, which can effectively inhibit the formation of carbon particles during diesel high-temperature cracking to promote the full combustion of diesel, mainly including sulfonate type, high-alkaline boron sulfonate type and salicylate type detergent. Small molecule amines represented by succinimide are the earliest used in ash-free detergent, followed by hydrocarbyl-substituted (poly) amines represented by polyisobutylene amine (PIBA), acyl (amino) imides represented by polyisobutylene succinimide, and polyether amine and Mannich base detergents have been developed. Acyl (amino) imide detergents have excellent cleaning capacity for deposits at the fuel injection nozzle, but cannot clean the deposits of high-temperature parts. Hydrocarbyl-substituted (poly) amines and Mannich base detergents can effectively clean the deposits at the fuel injection nozzle and intake valve, but increase the combustion chamber deposits. Polyether amine detergents can efficiently remove combustion chamber carbon deposits, but polyether amine has poor thermal stability and is almost completely decomposed when the temperature exceeds 300℃, which has poor cleaning effect on high-temperature parts such as intake valve.

[0004] Fuel borne catalyst (FBC) can reduce the activation energy of soot particles trapped in diesel particulate filter (DPF), make the chemical bond between soot particles easier to break, and realize DPF regeneration at a lower temperature. The currently used FBC catalysts are mainly iron-based and cerium-based metal organic compounds, in which the organic groups are mainly naphthenic acid, octanoic acid, oleic acid and the like. These conventional FBC catalysts have the disadvantages of poor dispersibility and single function. SUMMARY

[0005] To solve the problems in the prior art, the application provides a quaternary ammonium Mannich base, a quaternary ammonium Mannich base multifunctional fuel additive and a preparation method and application thereof.The multifunctional fuel additive comprises solvent oil, the quaternary ammonium Mannich base, a metal organic compound, an acetylenic diol polyether and an antioxidant.The multifunctional fuel additive has good dispersibility, can reduce the accumulation amount of vehicle engine carbon deposition, effectively reduce the balance point temperature, solve the passive regeneration failure of a diesel engine particulate filter (DPF), reduce the number of active regeneration and prolong the regeneration mileage.

[0006] One of the purposes of the application is to provide a quaternary ammonium Mannich base, the structural formula of which is shown as follows:

[0007]

[0008] wherein m = 10-90, preferably m = 15-80; n = 0-20, preferably n = 2-10; R1, R2 and R3 are the same or different and are independently H or C1-C4 alkyl; R4 is H, CH3 or C2H5; R5 is C3-C8 alkyl or aryl, preferably C3-C8 alkyl; R6 is CH3 or C2H5; and X is SO4 or CO3.

[0009] In one preferred embodiment of the application,

[0010] The quaternary ammonium Mannich base is prepared from raw materials comprising polyisobutylene, aromatic phenol, C2-C4 epoxide, N,N'-dimethyl-hydrocarbyl diamine, formaldehyde and a quaternization reagent.

[0011] The polyisobutylene has a molecular weight of 600-5000; and / or

[0012] The aromatic phenol is at least one of phenol, C1-C4 ortho or meta phenol; and / or

[0013] The N,N'-dimethyl-hydrocarbyl diamine is at least one of N,N'-dimethyl-alkyl diamine, N,N'-dimethyl-aryl diamine, preferably at least one of 3-dimethylamino-1-propylamine, N,N-dimethyl 1,4-butanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N-dimethyl-p-phenylenediamine, N,N-dimethyl-o-phenylenediamine, N,N-dimethyl-m-phenylenediamine; and / or

[0014] The C2-C4 epoxide is at least one of ethylene oxide, propylene oxide, butylene oxide; and / or

[0015] The quaternization reagent is at least one of dimethyl sulfate, diethyl sulfate, dimethyl carbonate.

[0016] In one preferred embodiment of the present application,

[0017] The preparation method of the quaternary ammonium Mannich base comprises:

[0018] (1) reacting an aromatic phenol with polyisobutylene in the presence of a catalyst to obtain a polyisobutylene aromatic phenol;

[0019] (2) reacting the polyisobutylene aromatic phenol obtained in step (1) with a C2-C4 epoxide in the presence of a basic catalyst to obtain a polyisobutylene phenyl polyether;

[0020] (3) reacting the polyisobutylene phenyl polyether obtained in step (2) with N,N'-dimethyl-hydrocarbyl diamine in the presence of formaldehyde and an acidic catalyst to obtain a polyisobutylene phenyl polyether Mannich base;

[0021] (4) reacting the polyisobutylene phenyl polyether Mannich base obtained in step (3) with a quaternary ammonium reagent to obtain the quaternary ammonium Mannich base.

[0022] In one preferred embodiment of the present application,

[0023] In step (1), the catalyst is at least one of boron trifluoride, boron trifluoride diethyl ether, aluminum trichloride, and zirconium tetrachloride, preferably, the molar ratio of the aromatic phenol, polyisobutylene, and catalyst is 1-3:1:0.1-0.6, more preferably 1-2:1:0.2-0.4; and / or,

[0024] In step (1), the reaction temperature is 50-130°C, preferably 80-120°C, and the reaction time is 2-12h, preferably 5-10h; and / or,

[0025] In step (2), the basic catalyst is at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium hydride, and sodium amide, preferably, the amount of the basic catalyst is 0.5-2% of the polyisobutylene aromatic phenol; and / or, the molar ratio of the polyisobutylene aromatic phenol and C2-C4 epoxide is 1:2-10; and / or,

[0026] In step (2), the reaction temperature is 90-140°C, preferably 90-110°C, the reaction time is 1-8h, preferably 5-8h, and the reaction pressure is 0.2-0.4MPa.

[0027] In one preferred embodiment of the present application,

[0028] In step (3), the acidic catalyst is at least one of sulfuric acid, phosphoric acid, p-toluene sulfonic acid, preferably the mass amount of the acidic catalyst is 0.2-2 times of the mass of the polyisobutylene phenyl polyether; and / or, the molar ratio of the polyisobutylene phenyl polyether, formaldehyde and N,N'-dimethyl-hydrocarbon diamine is 1:1-2:1-2; and / or,

[0029] In step (3), the reaction temperature is 60-130℃, preferably 90-110℃, and the reaction time is 3-12h, preferably 6-12h; and / or,

[0030] In step (4), the molar ratio of the polyisobutylene phenyl polyether Mannich base and the quaternization reagent is 1:0.95-1.2; and / or,

[0031] In step (4), the reaction temperature is 60-130℃, preferably 70-100℃, and the reaction time is 4-18h, preferably 6-12h.

[0032] The preparation method of the quaternized Mannich base can adopt the following specific technical solutions:

[0033] (1) Preparation of polyisobutylene aromatic phenol: aromatic phenol, high-activity polyisobutylene and catalyst are taken in a molar ratio of 1-3:1:0.1-0.6, the aromatic phenol and catalyst are dissolved in a solvent A in an amount of 0.2-2 times of the mass of the aromatic phenol, and the high-activity polyisobutylene is dissolved in the solvent A in an amount of 0.2-2 times of the mass of the high-activity polyisobutylene; the mixture of the aromatic phenol and catalyst is placed in a reaction kettle, nitrogen is blown to remove oxygen and water, and the mixture is heated to 50-130℃ under nitrogen atmosphere, the high-activity polyisobutylene solution is added dropwise into the reaction kettle through a constant-pressure dropping funnel, and the mixture is stirred at 50-130℃ for 2-12h; hot water is added to terminate the reaction, and the unreacted aromatic phenol and catalyst are removed with hot water, and the organic phase is dried with anhydrous sodium sulfate or anhydrous magnesium sulfate, filtered, and rotary evaporated to remove the solvent to obtain the polyisobutylene aromatic phenol;

[0034] The solvent A is at least one of toluene, ethylbenzene, xylene, dichloromethane, chloroform, and an alkane with a carbon number of 6-12;

[0035] (2) Preparation of polyisobutylene phenyl polyether: take polyisobutylene aromatic phenol and C2-C4 epoxide in a molar ratio of 1:2-10, respectively, add polyisobutylene aromatic phenol and 0.5%-2% of an alkaline catalyst by mass of the polyisobutylene aromatic phenol into a high-pressure reaction kettle, replace the air in the kettle with nitrogen for 3 times, vacuumize the kettle to a pressure of -0.05 to -0.095 MPa, and heat to 90-140°C, then slowly feed C2-C4 epoxide into the kettle through a conduit, the pressure in the kettle rises, and the pressure is controlled at 0.2-0.4 MPa, the reaction is carried out for 1-8 hours, when the pressure in the reaction kettle drops to 0 or below, the reaction is stopped, and the reaction product is taken out after the temperature drops to room temperature, neutralized to neutral with phosphoric acid, and filtered to remove insoluble substances, and the product is dried to obtain polyisobutylene phenyl polyether;

[0036] (3) Preparation of polyisobutylene phenyl polyether Mannich base: take polyisobutylene phenyl polyether, formaldehyde, and N,N'-dimethyl-hydrocarbyl diamine in a molar ratio of 1:1-2:1-2, put the polyisobutylene phenyl polyether and N,N'-dimethyl-hydrocarbyl diamine into a reaction kettle, dissolve in a solvent B in an amount of 0.2-2 times the mass of the polyisobutylene phenyl polyether, and add an acidic catalyst in an amount of 0.2-2 times the mass of the polyisobutylene phenyl polyether, stir uniformly under nitrogen protection, heat to 60-130°C, and drop formaldehyde, and the reaction is carried out for 3-12 hours, after the reaction is completed, wash the reaction product with hot water until the water phase is neutral, and remove the solvent by distillation under reduced pressure to obtain polyisobutylene phenyl polyether Mannich base;

[0037] The solvent B includes at least one of benzene, toluene, xylene, and ethylbenzene;

[0038] (4) Preparation of quaternized Mannich base: take polyisobutylene phenyl polyether Mannich base and a quaternization reagent in a molar ratio of 1:0.95-1.2, dissolve the polyisobutylene phenyl polyether Mannich base in a solvent C in an amount of 0.2-2 times the mass of the polyisobutylene phenyl polyether Mannich base, and put the polyisobutylene phenyl polyether Mannich base solution into a reaction kettle, heat to 60-130°C, drop the quaternization reagent into the kettle, and the reaction is carried out for 4-18 hours, after the reaction is completed, remove the solvent and unreacted quaternization reagent by rotary evaporation, and the residue is quaternized polyisobutylene phenyl polyether Mannich base, simply referred to as quaternized Mannich base;

[0039] The solvent C is at least one of methanol, ethanol, propanol, butanol, and isopropanol.

[0040] The second purpose of the present application is to provide a quaternized Mannich base multifunctional fuel additive, which includes the following components:

[0041] 1) solvent oil;

[0042] 2) the quaternized Mannich base of the first purpose of the present application;

[0043] 3) metal organic compound;

[0044] 4) acetylenic diol polyether;

[0045] 5) antioxidant.

[0046] In a preferred embodiment of the present application,

[0047] Each component is based on 100 parts by weight of solvent oil,

[0048] 100 parts by weight of solvent oil;

[0049] 10 to 50 parts by weight of quaternary ammonium Mannich base; preferably 30 to 40 parts by weight;

[0050] 0.1 to 15 parts by weight of metal organic compound; preferably 1 to 10 parts by weight; more preferably 6 to 10 parts by weight;

[0051] 0.5 to 10 parts by weight of acetylenic diol polyether; preferably 2 to 8 parts by weight;

[0052] 0.1 to 2 parts by weight of antioxidant; preferably 0.5 to 2 parts by weight.

[0053] In a preferred embodiment of the present application,

[0054] The structure of the acetylenic diol polyether is as follows:

[0055]

[0056] wherein R2 and R3 are methyl, R1 and R4 are the same or different and are independently selected from alkyl groups containing 3 to 8 carbon atoms; m1 and m2 are the same or different, m1 + m2 = 0 to 16, preferably m1 + m2 = 2 to 10, n1 and n2 are the same or different, n1 + n2 = 0 to 20, preferably n1 + n2 = 2 to 10, and m1, m2, n1, n2 are not simultaneously 0; and / or,

[0057] The solvent oil is at least one of alkanes solvent oil with a boiling range of 60 to 200°C, aromatic solvent oil with a boiling range of 60 to 200°C, C6 to C 12 alkyl alcohol; preferably one of 60# solvent oil, 120# solvent oil, 200# solvent oil; and / or,

[0058] The metal organic compound is at least one of iron naphthenate, iron saturated or unsaturated fatty acid with a carbon number of 6 to 22, cerium naphthenate, cerium petroleum acid, cerium saturated or unsaturated fatty acid with a carbon number of 6 to 22, iron crown ether complex, iron porphyrin complex, platinum crown ether complex, platinum porphyrin complex, ferrocene; and / or,

[0059] The antioxidant is at least one of phenylenediamine, alkyl phenylenediamine, p-tert-butyl phenol, 2,6-di-tert-butyl-p-cresol.

[0060] The multifunctional fuel additive of the present application can also be added with conventional components in the field, such as propylene glycol polyether, glycerol polyether, nonyl phenol polyether, etc., in conventional amounts, which can be adjusted by the skilled person according to the actual situation.

[0061] The third object of the present application is to provide a preparation method of the quaternary ammonium Mannich base multifunctional fuel additive of the second object of the present application, which comprises mixing the components including solvent oil, quaternary ammonium Mannich base, metal organic compound, acetylenic diol polyether and antioxidant in the amounts as described above to obtain the quaternary ammonium Mannich base multifunctional fuel additive.

[0062] The fourth object of the present application is to provide the use of the multifunctional fuel additive of the second object of the present application or the fuel additive prepared by the method of the third object of the present application in diesel vehicle fuel, which is used in a proportion of 1 / 10000 to 1 / 10 of the fuel.

[0063] The quaternary ammonium Mannich base of the present application has multiple functional groups, among which the polyisobutylene phenyl group is a branched lipophilic group; the polyether (polyoxyethylene ether, polyoxypropylene ether or polyoxybutylene ether) has C-O-C group and terminal hydroxyl group, which can form hydrogen bond with sludge or deposit; the quaternary ammonion head is a cation, while the sludge or deposit is usually negatively charged, and the electrostatic interaction makes the quaternary ammonium Mannich base have stronger interaction with the sludge or deposit; the above hydrogen bond interaction and electrostatic interaction make the quaternary ammonium Mannich base better disperse the sludge and deposit, so that it is solubilized and dispersed into fine particles in the fuel; on the other hand, the quaternary ammonion head of the quaternary ammonium Mannich base can be adsorbed on the surface of the wall by electrostatic interaction, so as to hydrophobize the surface of the wall and inhibit the deposition of sludge and other polar substances.

[0064] The beneficial effects of the present application are as follows:

[0065] The quaternary ammonium Mannich base multifunctional fuel additive of the present application has good solubility when used, and not only has good dispersibility, but also has the effect of reducing the accumulation amount of vehicle engine carbon deposit, and can effectively reduce the balance point temperature, solve the failure of passive regeneration of diesel engine particulate filter (DPF), reduce the number of active regeneration, and prolong the regeneration mileage; in addition, the acetylenic diol polyether has low foaming and defoaming properties, and is not easy to foam during use, and the acetylenic diol surfactant can be firmly adsorbed on the metal surface to inhibit the corrosion of metal walls such as exhaust pipes at high temperature. DETAILED DESCRIPTION

[0066] The present application will be described in detail below with reference to specific examples. It is necessary to point out that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments of the present application made by those skilled in the art according to the content of the present application still fall within the scope of protection of the present application.

[0067] The raw materials used in the examples are all conventional commercially available raw materials.

[0068] Preparation of decynediol polyoxyethylene (4) ether in Example 1:

[0069] (1) Preparation of nano-catalyst (Mg / Al / Co composite metal oxide catalyst):

[0070] A mixed solution I of NaOH and Na2CO3 with a molar concentration of 2:1 (the volume of the mixed solution I is 100 mL, and the molar concentration of Na2CO3 is 0.5 mol / L) is prepared, a mixed solution II of Mg(NO3)2 and Al(NO3)3 with a molar concentration of 3:1 (the volume of the mixed solution II is 100 mL, and the molar concentration of Al(NO3)3 is 0.5 mol / L) is prepared, and a CoNO3 solution with the same volume as the mixed solution II is prepared, and the concentration of the CoNO3 solution is 1 / 5 of the molar concentration of Al(NO3)3 in the mixed solution II; the CoNO3 solution is kept at 60°C, and the mixed solution I and the mixed solution II are simultaneously added dropwise into the CoNO3 solution under vigorous stirring, and the pH value during the dropwise addition process is controlled to be 8.5-9.5; after the dropwise addition is completed, the reaction liquid is kept at constant temperature and stirred for 30 min, and then is put into an oven at 100°C for crystallization for 12 hours; the slurry after crystallization is filtered, washed until the filtrate is neutral, and the filter cake is put into an oven for drying; the dried solid is ball-milled to obtain the Mg / Al / Co composite metal oxide catalyst.

[0071] (2) 0.2 mol of tetramethyl decynediol (abbreviated as TMAD10, and the structural formula of tetramethyl decynediol is: wherein R2 and R3 are -CH3, and R1 and R4 are both -CH2CH(CH3)2) is put into a high-pressure reaction kettle together with 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained in step (1) above, and is stirred uniformly, the air in the kettle is replaced with nitrogen for 3 times, the high-pressure reaction kettle is vacuumed for 30 min at 80°C by using a vacuum pump, and the vacuuming is stopped; 0.8 mol of ethylene oxide is slowly introduced into the reaction kettle through a feeding pipe, the temperature of the reaction kettle is increased to 115°C, the pressure in the kettle is controlled to be about 0.20 MPa, and the stirring reaction is carried out for 4 h; after the pressure in the reaction kettle is reduced to negative pressure, the reaction is stopped, the reaction mixture is taken out, and the nano-catalyst is removed by using a microporous membrane to obtain decynediol polyoxyethylene (4) ether (TMAD10-EO4);

[0072] The structural formula of the decynediol polyoxyethylene (4) ether (TMAD10-EO4) is as follows: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=4, and n1+n2=0.

[0073] Preparation of decynediol polyoxyethylene (8) polyoxypropylene (4) ether in Example 2:

[0074] (1) The amount of the above-mentioned ethylene oxide is changed to 1.6 mol to obtain decynediol polyoxyethylene (8) ether (TMAD10-EO8) with an EO (C2H4O) number of 8;

[0075] The structural formula of the decynediol polyoxyethylene (8) ether (TMAD10-EO8) is as follows: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, and n1+n2=0.

[0076] (2) 0.1 mol of TMAD10-EO8 and 0.8 g of the Mg / Al / Co composite metal oxide catalyst obtained in the above-mentioned step (1) are put into a high-pressure reaction kettle, stirred uniformly, and the air in the kettle is replaced with nitrogen for 3 times. The high-pressure reaction kettle is vacuumed for 30 min at 80°C with a vacuum pump, and the vacuuming is stopped. 0.4 mol of propylene oxide is introduced into the reaction kettle through a feeding pipe, and the temperature of the reaction kettle is increased to 125°C. The pressure in the kettle is controlled at about 0.3 MP, and the stirring reaction is carried out for 12 h. After the pressure in the reaction kettle is reduced to negative pressure, the reaction is stopped, and the reaction mixture is taken out. The nano-catalyst is removed by microporous membrane filtration to obtain decynediol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4).

[0077] The structural formula of the decynediol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4) is as follows: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, and n1+n2=4.

[0078] Preparation of dodecynediol polyoxyethylene (8) ether in Example 3:

[0079] The tetramethyl decynediol in the above-mentioned step is replaced by tetramethyl dodecynediol (abbreviated as TMAD12, and the structural formula of tetramethyl dodecynediol is as follows: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH2CH(CH3)2, and the feeding amounts of ethylene oxide and propylene oxide are controlled to obtain dodecynediol polyoxyethylene (8) ether (TMAD12-EO8) with an EO number of 8.

[0080] Example 1

[0081] Preparation of polyisobutylene phenol: phenol, high activity polyisobutylene (BASF, molecular weight 1000) and boron trifluoride ether were taken in a molar ratio of 2:1:0.3, phenol and catalyst were dissolved in xylene with a mass of 0.8 times that of phenol, and high activity polyisobutylene was dissolved in xylene with a mass of 0.8 times that of high activity polyisobutylene; the mixture of phenol and catalyst was placed in a reaction kettle, nitrogen was used to remove oxygen and water, and the temperature was raised to 80°C under a nitrogen atmosphere; the high activity polyisobutylene solution was added to the reaction kettle through a constant pressure dropping funnel, and the reaction was stirred at 80°C for 8h; hot water was added to terminate the reaction, and hot water was used to remove unreacted phenol and catalyst, and the organic phase was dried with anhydrous sodium sulfate; filtration was performed, and the filtrate was obtained after the solvent was removed by rotary evaporation to obtain polyisobutylene phenol;

[0082] Preparation of polyisobutylene phenyl polyoxyethylene ether: polyisobutylene phenol and ethylene oxide were taken in a molar ratio of 1:4, respectively, polyisobutylene phenol and 1% sodium hydroxide of the mass of polyisobutylene phenol were added to a high-pressure reaction kettle, the kettle was purged with nitrogen three times, the kettle was vacuumized to a pressure of -0.09 MPa, and the temperature was raised to 100°C; after stopping vacuumization, ethylene oxide was slowly introduced into the kettle through a conduit, the pressure in the kettle rose, and the pressure was controlled at 0.25 MPa, the reaction was carried out for 6h, and when the pressure in the reaction kettle dropped to 0 or below, the reaction was stopped, and after the temperature dropped to room temperature, the reaction product was taken out, neutralized to neutral with phosphoric acid, insoluble substances were removed by filtration, and the product was dried to obtain polyisobutylene phenyl polyoxyethylene ether (4);

[0083] Preparation of polyisobutylene phenyl polyoxyethylene ether (4) Mannich base: polyisobutylene phenyl polyoxyethylene ether, formaldehyde and 3-dimethylamino-1-propanamine were taken in a molar ratio of 1:1.5:1.5; polyisobutylene phenyl polyoxyethylene ether and 3-dimethylamino-1-propanamine were placed in a reaction kettle, dissolved in xylene with the same mass as polyisobutylene phenyl polyoxyethylene ether, and a catalyst of p-toluenesulfonic acid with a mass of 1.2 times that of polyisobutylene phenyl polyoxyethylene ether was added, and stirred uniformly under nitrogen protection; the temperature was raised to 100°C, formaldehyde was added dropwise, and the reaction was carried out for 8h; after the reaction was completed, the reaction product was washed with hot water until the aqueous phase was neutral, and the solvent was removed by vacuum distillation to obtain polyisobutylene phenyl polyoxyethylene ether (4) Mannich base;

[0084] Preparation of quaternary ammonium mannhich base: take polyisobutylene phenyl polyoxyethylene ether (4) mannhich base and dimethyl sulfate in a molar ratio of 1:0.99, dissolve the polyisobutylene phenyl polyoxyethylene ether (4) mannhich base in isopropyl alcohol with a mass of 1.2 times that of the polyisobutylene phenyl polyoxyethylene ether (4) mannhich base, and place the polyisobutylene phenyl polyoxyethylene ether (4) mannhich base solution in a reaction kettle, heat to 80°C, and add dimethyl sulfate dropwise into the kettle, react for 8h, and after the reaction is completed, remove the solvent and unreacted quaternary ammonium reagent by rotary evaporation, and the residue is the quaternary ammonium polyisobutylene phenyl polyoxyethylene ether (4) mannhich base, which is referred to as quaternary ammonium mannhich base (EO4) for short;

[0085] The structural formula of the quaternary ammonium mannhich base (EO4) obtained above is as follows:

[0086] wherein m = 17; R1, R2, R3, R4 are H; R5 is C3H6; R6 is CH3; and X is SO4;

[0087] Preparation of quaternary ammonium mannhich base multifunctional fuel additive:

[0088] Quaternary ammonium mannhich base (EO4) 35 parts by weight, 6# solvent oil 100 parts by weight, iron octanoate 8 parts by weight, decyne glycol polyoxyethylene (4) ether 2.0 parts by weight, and p-phenylenediamine 0.5 parts by weight are uniformly mixed at 50°C to prepare multifunctional fuel additive i#.

[0089] Solubility of i# multifunctional fuel additive: after the multifunctional fuel additive i# is mixed with diesel oil at a volume ratio of 1:10, it is well dispersed, and no stratification or precipitation is observed after 12 months of storage.

[0090] The low-temperature dispersing performance of the multifunctional fuel additive is tested by the oil sludge spot dispersion test method, and the oil sludge spot dispersion value SDT is used to evaluate the low-temperature dispersing performance of the dispersant. The larger the SDT value, the better the oil sludge dispersing performance of the dispersant at low temperature. According to the SH / T 0623-95 procedure, the oil sludge dispersing test is carried out. Without adding multifunctional fuel additive, the STD value is 20. After adding 12% multifunctional fuel additive i#, the STD value rises to 42, indicating that the i# multifunctional fuel additive has good oil sludge dispersing performance.

[0091] The nozzle coking detection is carried out according to the method and technical requirements specified in SH / T 0764 "Diesel Engine Nozzle Coking Test Method (XUD-9 Method)". The average air flow loss of diesel oil without adding multifunctional fuel additive is 85.5% when the needle valve lift of cylinders 1-4 is 0.1 mm. After adding i# multifunctional fuel additive at a volume ratio of fuel additive to diesel oil of 1:1000, the average air flow loss of cylinders 1-4 is 27.1% when the needle valve lift is 0.1 mm, indicating that the multifunctional fuel additive has excellent effect on removing engine carbon deposits.

[0092] A bench test was conducted using a Weichai WP13 heavy-duty diesel engine. The bench test device included a diesel engine, a dynamometer, an aftertreatment device system including a DOC, a particulate filter (DPF), and an SCR, and a data acquisition system. The engine operating point was adjusted to adjust the exhaust gas temperature, and then the DPF deposit equilibrium point temperature was measured. The measurement started at 300°C and increased by 20°C each time until 440°C. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference between the two ends of the DPF. For the same aftertreatment device (DPF including a catalyst coating), before adding the fuel additive, the equilibrium point temperature was 400°C. After adding i# multifunctional fuel additive to diesel at a volume ratio of 1:100, the equilibrium point temperature decreased by 84°C.

[0093] A real vehicle test was conducted using a small truck equipped with a 2.0L CTI diesel engine. The truck had a DPF volume of 3.3L and a maximum carbon loading of 20g. The vehicle regeneration interval mileage was about 500km. During the test, i# multifunctional fuel additive was added to the diesel at a concentration of 10mg / kg (based on iron content). Before the test, the vehicle was expected to trigger regeneration after driving about 400km. After adding i# multifunctional fuel additive, the DPF actually triggered regeneration after driving about 4200km, greatly extending the DPF regeneration interval mileage.

[0094] Example 2

[0095] Preparation of polyisobutylene phenol: phenol, high-activity polyisobutylene (BASF, molecular weight 2300), and boron trifluoride ether were taken in a molar ratio of 1.2:1:0.3. The phenol and boron trifluoride ether catalyst were dissolved in toluene with a mass of 1.2 times that of the phenol, and the high-activity polyisobutylene was dissolved in toluene with a mass of 0.6 times that of the high-activity polyisobutylene. The mixture of phenol and catalyst was placed in a reaction kettle, and nitrogen was used to remove oxygen and water. The reaction kettle was heated to 100°C under a nitrogen atmosphere, and the high-activity polyisobutylene solution was added dropwise to the reaction kettle through a constant-pressure dropping funnel. The reaction was stirred at 100°C for 8h. Hot water was added to terminate the reaction, and hot water was used to remove unreacted phenol and catalyst. The organic phase was dried with anhydrous sodium sulfate. After filtration, the filtrate was concentrated by rotary evaporation to obtain polyisobutylene phenol.

[0096] Preparation of polyisobutylene benzene polyoxypropylene ether: polyisobutylene phenol and propylene oxide were taken in a molar ratio of 1:8, polyisobutylene phenol and 1% sodium hydroxide of its mass were added into a high-pressure reaction kettle, the air in the kettle was replaced with nitrogen for 3 times, the kettle was vacuumized to a pressure of -0.09 MPa, and was heated to 100°C; after the vacuumization was stopped, propylene oxide was slowly fed into the kettle through a conduit, the pressure in the kettle rose, the pressure was controlled to be 0.25 MPa, the reaction was carried out for 8 hours, when the pressure in the reaction kettle dropped to below 0, the reaction was stopped, after the temperature dropped to room temperature, the reaction product was taken out, neutralized to neutral with phosphoric acid, the insoluble substances were removed by filtration, and the product was dried to obtain polyisobutylene benzene polyoxypropylene ether (8);

[0097] Preparation of polyisobutylene benzene polyoxypropylene ether (8) Mannich base: polyisobutylene benzene polyoxypropylene ether, formaldehyde and 3-dimethylamino-1-propanamine were taken in a molar ratio of 1:1.2:1.2; the polyisobutylene benzene polyoxypropylene ether and 3-dimethylamino-1-propanamine were placed in a reaction kettle, dissolved in toluene with the same mass as the polyisobutylene benzene polyoxypropylene ether, and 0.8 times the mass of the polyisobutylene benzene polyoxypropylene ether of p-toluene sulfonic acid catalyst was added, stirred uniformly under nitrogen protection; heated to 100°C, and formaldehyde was added dropwise, the reaction was carried out for 8 hours; after the reaction was completed, the reaction product was washed with hot water until the water phase was neutral, and the solvent was removed by distillation under reduced pressure to obtain polyisobutylene benzene polyoxypropylene ether (8) Mannich base;

[0098] Preparation of quaternary ammonium Mannich base: polyisobutylene benzene polyoxypropylene ether (8) Mannich base and diethyl sulfate were taken in a molar ratio of 1:1.05, the polyisobutylene benzene polyoxypropylene ether (8) Mannich base was dissolved in 1.5 times the mass of ethanol, and the polyisobutylene benzene polyoxypropylene ether (8) Mannich base solution was placed in a reaction kettle, heated to 80°C, diethyl sulfate was added dropwise into the kettle, the reaction was carried out for 8 hours, after the reaction was completed, the solvent and unreacted diethyl sulfate were removed by rotary evaporation, and the residue was quaternary ammonium polyisobutylene benzene polyoxypropylene ether (8) Mannich base, which was referred to as quaternary ammonium Mannich base (PO8);

[0099] The structural formula of the quaternary ammonium Mannich base (PO8) obtained above is as follows:

[0100] Wherein, m=41; n=8; R1, R2, R3 are H; R4 is CH3; R5 is C3H6; R6 is C2H5; X is SO4;

[0101] Preparation of quaternary ammonium Mannich base multifunctional fuel additive: quaternary ammonium Mannich base (PO8) 40 parts by weight, 120# solvent oil 100 parts by weight, cerium naphthenate 8 parts by weight, decyne glycol polyoxyethylene (8) polyoxypropylene (4) ether 8 parts by weight, and p-tert-butyl phenol 0.8 parts by weight were uniformly mixed at 40°C to prepare a multifunctional fuel additive ii.

[0102] The multifunctional fuel additive ii# is mixed with diesel fuel at a volume ratio of 1:10, and is well dispersed, and has no stratification or precipitation after being placed for 12 months.

[0103] The low-temperature dispersing performance of the multifunctional fuel additive is tested by using the oil sludge spot dispersion test method, and the oil sludge spot dispersion value SDT is used to evaluate the low-temperature dispersing performance of the dispersant. The larger the SDT value, the better the oil sludge dispersing performance of the dispersant at low temperature. The oil sludge dispersing test is carried out according to the SH / T 0623-95 procedure experiment. Without the multifunctional fuel additive, the STD value is 20. After adding 12% multifunctional fuel additive ii#, the STD value rises to 58, indicating that the multifunctional fuel additive ii# has good oil sludge dispersing performance.

[0104] The nozzle coking detection is carried out according to the method and technical requirements specified in SH / T 0764 "Diesel Engine Nozzle Coking Test Method (XUD-9 Method)". When the needle valve lift of cylinders 1-4 is 0.1 mm, the average air flow loss of diesel fuel without adding multifunctional fuel additive is 85.5%. After adding multifunctional fuel additive ii# at a volume ratio of 1:1000, the average air flow loss of cylinders 1-4 when the needle valve lift is 0.1 mm is 22.5%, and the multifunctional fuel additive has excellent effect of removing engine carbon deposit.

[0105] The bench test is carried out by using Weichai WP13 heavy-duty diesel engine. The bench test device includes diesel engine, dynamometer, aftertreatment device system including DOC, particulate filter (DPF) and SCR, and data acquisition system. The engine operating point is adjusted to adjust the exhaust gas temperature, and then the DPF deposit equilibrium point temperature is measured. The measurement starts from 300°C, increases by 20°C each time, and ends at 440°C. The continuous passive regeneration equilibrium point temperature is determined by measuring the pressure difference change between the two ends of the DPF. For the same aftertreatment device (DPF including catalyst coating), before adding the fuel additive, the equilibrium point temperature is 400°C. After adding multifunctional fuel additive ii# to diesel fuel at a volume ratio of 1:100, the equilibrium point temperature is reduced by 90°C.

[0106] The real vehicle test is carried out by using a small truck equipped with a 2.0L CTI diesel engine. The volume of the DPF of the truck is 3.3L, and the maximum carbon load is 20g. The vehicle regeneration interval driving distance is about 500km. During the test, multifunctional fuel additive i# is added to the diesel fuel at a concentration of 10mg / kg (calculated according to the cerium content). Before the test, it is estimated that the vehicle will travel about 400km before the DPF triggers regeneration. After adding multifunctional fuel additive ii#, the DPF triggers regeneration after actually traveling about 4600km, greatly extending the DPF regeneration interval distance.

[0107] Example 3

[0108] Preparation of polyisobutylene phenol: phenol, high activity polyisobutylene (BASF, molecular weight 4000) and boron trifluoride ether were taken in a molar ratio of 1:1:0.3, phenol and catalyst were dissolved in octane with the same mass as phenol, high activity polyisobutylene was dissolved in octane with the same mass as itself; the mixture of phenol and catalyst was placed in a reaction kettle, oxygen and water were removed by nitrogen, heated to 120°C under nitrogen atmosphere, high activity polyisobutylene solution was added to the reaction kettle through a constant pressure dropping funnel, stirred at 120°C for 6h; the reaction was terminated by adding hot water, and the unreacted phenol and catalyst were removed with hot water, the organic phase was dried with anhydrous magnesium sulfate; filtration, the filtrate was obtained after removing the solvent by rotary evaporation to obtain polyisobutylene phenol;

[0109] Preparation of polyisobutylene phenyl polyoxybutylene ether: polyisobutylene phenol and epoxy butane were taken in a molar ratio of 1:6, respectively, polyisobutylene phenol and 1% potassium hydroxide of its mass were added to a high-pressure reaction kettle, the air in the kettle was replaced with nitrogen for 3 times, the kettle was vacuumed to a pressure of-0.09MPa, and the temperature was raised to 100°C; after stopping vacuuming, epoxy butane was slowly introduced into the kettle through a conduit, the pressure in the kettle rose, the pressure was controlled at 0.25MPa, and the reaction was carried out for 6h, when the pressure in the reaction kettle dropped to 0 or below, the reaction was stopped, and after the temperature dropped to room temperature, the reaction product was taken out, neutralized to neutral with phosphoric acid, insoluble substances were removed by filtration, and the product was dried to obtain polyisobutylene phenyl polyoxybutylene ether (6);

[0110] Preparation of polyisobutylene phenyl polyoxybutylene ether (6) mannich base: polyisobutylene phenyl polyoxybutylene ether (6), formaldehyde and 3-dimethylamino-1-propanamine were taken in a molar ratio of 1:1.5:1.5; polyisobutylene phenyl polyoxybutylene ether (6) and 3-dimethylamino-1-propanamine were placed in a reaction kettle, dissolved in dimethylbenzene with the same mass as polyisobutylene phenyl polyoxybutylene ether (6), and catalyst of sulfuric acid with 0.6 times the mass of polyisobutylene phenyl polyoxybutylene ether (6) was added, stirred uniformly under nitrogen protection; the temperature was raised to 100°C, formaldehyde was added dropwise, and the reaction was carried out for 10h; after the reaction was completed, the reaction product was washed with hot water until the aqueous phase was neutral, and the solvent was removed by vacuum distillation to obtain polyisobutylene phenyl polyoxybutylene ether (6) mannich base;

[0111] Preparation of quaternary ammonium mannich base: polyisobutylene phenyl polyoxybutylene ether (6) mannich base and dimethyl carbonate were taken in a molar ratio of 1:1.2, polyisobutylene phenyl polyoxybutylene ether (6) mannich base was dissolved in isopropanol with 1.2 times the mass of itself, and the polyisobutylene phenyl polyoxybutylene ether (6) mannich base solution was placed in a reaction kettle, the temperature was raised to 90°C, dimethyl carbonate was added dropwise to the kettle, the reaction was carried out for 10h, and after the reaction was completed, the solvent and unreacted dimethyl carbonate were removed by rotary evaporation, the residue was quaternary ammonium polyisobutylene phenyl polyoxybutylene ether (6) mannich base, which was simply referred to as quaternary ammonium mannich base (BO6);

[0112] The structural formula of the obtained quaternary ammonium Mannich base (BO6) is as follows:

[0113] wherein m = 71; n = 6; R1, R2, and R3 are H; R4 is C2H5; R5 is C3H6; R6 is CH3; and X is CO3;

[0114] Preparation of the quaternary ammonium Mannich base multifunctional fuel additive: 40 parts by weight of the quaternary ammonium Mannich base (BO6), 100 parts by weight of 200# solvent oil, 10 parts by weight of iron oleate, 5 parts by weight of dodecynediol polyoxyethylene (8) ether, and 1 part by weight of 2,6-di-tert-butyl-p-cresol are uniformly mixed at 50°C to prepare the multifunctional fuel additive iii#.

[0115] Solubility of the multifunctional fuel additive iii#: After the multifunctional fuel additive iii# is mixed with diesel oil at a volume ratio of 1:10, it is well dispersed and no stratification or precipitation is observed after 12 months of storage.

[0116] The low-temperature dispersing performance of the multifunctional fuel additive is tested by the oil sludge spot dispersion test method, and the low-temperature dispersing performance of the dispersant is evaluated by the oil sludge spot dispersion value SDT. The larger the SDT value, the better the oil sludge dispersing performance of the dispersant at low temperature. The oil sludge dispersing performance test is carried out according to the SH / T 0623-95 procedure. Without the multifunctional fuel additive, the STD value is 20. After 12% of the multifunctional fuel additive iii# is added, the STD value rises to 52, indicating that the multifunctional fuel additive iii# has good oil sludge dispersing performance.

[0117] The nozzle coking detection is carried out according to the method and technical requirements specified in SH / T 0764 "Diesel Engine Nozzle Coking Test Method (XUD-9 Method)". When the needle valve lift of cylinders 1-4 is 0.1 mm, the average air flow loss of diesel oil without the multifunctional fuel additive is 85.5%. After the multifunctional fuel additive iii# is added at a volume ratio of 1:1000, the average air flow loss of cylinders 1-4 when the needle valve lift is 0.1 mm is 23.8%, indicating that the multifunctional fuel additive has excellent effect of removing engine carbon deposits.

[0118] A bench test was conducted on a Weichai WP13 heavy-duty diesel engine. The test device included a diesel engine, a dynamometer, an aftertreatment device system including a DOC, a particulate filter (DPF), and an SCR, and a data acquisition system. The engine operating point was adjusted to adjust the exhaust gas temperature, and then the DPF deposit equilibrium point temperature was measured. The measurement started at 300°C and increased by 20°C each time until 440°C. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference between the two ends of the DPF. For the same aftertreatment device (DPF including a catalyst coating), before adding the fuel additive, the equilibrium point temperature was 400°C. After adding the iii# multifunctional fuel additive to the diesel fuel at a volume ratio of 1:100, the equilibrium point temperature decreased by 89°C.

[0119] A real vehicle test was conducted on a small truck equipped with a 2.0L CTI diesel engine. The truck's DPF had a volume of 3.3L and a maximum carbon loading of 20g. The vehicle's regeneration interval was about 500km. During the test, the iii# multifunctional fuel additive was added to the diesel fuel at a concentration of 10mg / kg (based on iron content). Before the test, the vehicle was expected to travel about 400km before the DPF triggered regeneration. After adding the iii# multifunctional fuel additive, the DPF actually triggered regeneration after traveling about 4700km, greatly extending the DPF regeneration interval.

[0120] Comparative Example 1

[0121] Preparation of polyisobutylene benzyl polyoxyethylene ether (4) Mannich base multifunctional fuel additive:

[0122] Polyisobutylene benzyl polyoxyethylene ether (4) Mannich base (i.e., the polyisobutylene benzyl polyoxyethylene ether (4) Mannich base prepared in the third step of Example 1) 35 parts by weight, 6# solvent oil 100 parts by weight, iron octanoate 8 parts by weight, decyne glycol polyoxyethylene ether (4) ether 2.0 parts by weight, p-phenylenediamine 0.5 parts by weight, were uniformly mixed at 50°C to prepare multifunctional fuel additive iv#.

[0123] Solubility of iv# multifunctional fuel additive: After mixing the multifunctional fuel additive iv# with diesel fuel at a volume ratio of 1:10, it was well dispersed and had no layering or precipitation after 12 months.

[0124] The low-temperature dispersing performance of the multifunctional fuel additive was tested using the oil sludge spot dispersion test method. The low-temperature dispersing performance of the dispersant was evaluated using the oil sludge spot dispersion value SDT. The larger the SDT value, the better the oil sludge dispersing performance of the dispersant at low temperatures. The oil sludge dispersing test was carried out according to the SH / T 0623-95 procedure. Without the multifunctional fuel additive, the STD value was 20. After adding 12% multifunctional fuel additive iv#, the STD value increased to 41, indicating that the iv# multifunctional fuel additive had good oil sludge dispersing performance.

[0125] The nozzle coking detection was carried out according to the method and technical requirements specified in SH / T 0764 Diesel Engine Nozzle Coking Test Method (XUD-9 Method), and the average air flow loss of diesel 1-4 cylinder needle valve lift 0.1 mm without adding the multifunctional fuel additive was 85.5%; after adding the multifunctional fuel additive iv to diesel at a volume ratio of 1:1000, the average air flow loss of 1-4 cylinder needle valve lift 0.1 mm was 30.3%, and the multifunctional fuel additive had a good effect of removing engine carbon deposition.

[0126] A WP13 heavy-duty diesel engine of Weichai was used for bench test, and the bench test device included a diesel engine, a dynamometer, an aftertreatment device system including a DOC, a particulate filter (DPF) and an SCR, and a data acquisition system. The engine operating point was adjusted to adjust the exhaust gas temperature, and then the DPF deposit equilibrium point temperature was measured, starting from 300℃, increasing by 20℃ each time, and ending at 440℃. The continuous passive regeneration equilibrium point temperature was determined by measuring the pressure difference change of the two ends of the DPF. For the same aftertreatment device (the DPF includes a catalyst coating), before adding the fuel additive, the equilibrium point temperature was 400℃, and after adding the multifunctional fuel additive iv to diesel at a volume ratio of 1:100, the equilibrium point temperature was reduced by 80℃.

[0127] A small truck equipped with a 2.0L CTI diesel engine was used for real vehicle test, the volume of the DPF of the truck was 3.3L, the maximum carbon loading was 20g, and the vehicle regeneration interval driving mileage was about 500km. During the test, the multifunctional fuel additive iv was added to diesel at a concentration of 10mg / kg (calculated according to the iron content). Before the test, it was predicted that the DPF would trigger regeneration after driving about 400km, and after adding the multifunctional fuel additive iv, the DPF actually triggered regeneration after driving about 4000km, which prolonged the DPF regeneration interval mileage.

[0128] As can be seen from Examples 1-3 and Comparative Example 1, the multifunctional fuel additive containing quaternary ammonium Mannich base of the present application not only has good dispersibility and an effect of reducing the accumulation amount of vehicle engine carbon deposition, but also can effectively reduce the equilibrium point temperature, solve the passive regeneration failure of the diesel engine particulate filter (DPF), reduce the number of active regeneration, and prolong the regeneration mileage.

Claims

1. A quaternized Mannich base multifunctional fuel additive, comprising the following components: 1) Solvent oil; 2) Quaternized Mannich base; the quaternized Mannich base has the following structural formula: in, m = 10~90; n = 2~20; R1, R2, and R3 may be the same or different, and are independently H or C1-C4 alkyl groups; R4 is H, CH3, or C2H5; R5 is C3-C8 alkyl or aryl; R6 is CH3 or C2H5; X is SO4 or CO3; 3) Organometallic compounds; 4) Acetylene glycol polyether; 5) Antioxidants; Each component is based on 100 parts by weight of solvent oil. 100 parts by weight of solvent oil; 10-50 parts by weight of quaternized Mannich base; Organometallic compounds, 0.1 to 15 parts by weight; 0.5-10 parts by weight of acetylacetonate diol polyether; Antioxidant 0.1~2 parts by weight.

2. The quaternized Mannich base multifunctional fuel additive as described in claim 1, characterized in that: The m=15~80; n=2~10; R5 is a C3-C8 alkyl group.

3. The quaternized Mannich base multifunctional fuel additive as described in claim 1, characterized in that: The quaternized Mannich base is prepared from raw materials comprising the following components: polyisobutylene, aromatic phenol, C2-C4 epoxide, N,N'-dimethyl-alkyldiamine, formaldehyde and quaternizing agent; The polyisobutylene has a molecular weight of 600-5000; and / or, The aromatic phenol is at least one of phenol, ortho- or meta-phenol of C1-C4; and / or, The N,N'-dimethyl-alkyl diamine is at least one selected from N,N'-dimethyl-alkyl diamine and N,N'-dimethyl-aryl diamine; and / or The C2-C4 epoxide is at least one selected from ethylene oxide, propylene oxide, and butane oxide; and / or, The quaternizing agent is at least one of dimethyl sulfate, diethyl sulfate, and dimethyl carbonate.

4. The quaternized Mannich base multifunctional fuel additive as described in claim 3, characterized in that: The N,N'-dimethyl-alkyldiamine is at least one of 3-dimethylamino-1-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N-dimethyl-p-phenylenediamine, N,N-dimethyl-o-phenylenediamine, and N,N-dimethyl-m-phenylenediamine.

5. The quaternized Mannich base multifunctional fuel additive as described in claim 3, characterized in that: The method for preparing the quaternized Mannich base includes: (1) Aromatic phenols are reacted with polyisobutylene in the presence of a catalyst to obtain polyisobutylene aromatic phenols; (2) The polyisobutylene aromatic phenol obtained in step (1) is reacted with C2-C4 epoxide in the presence of an alkaline catalyst to obtain polyisobutylene phenyl polyether. (3) The polyisobutylene phenyl polyether obtained in step (2) is reacted with N,N'-dimethyl-hydrodiamine in the presence of formaldehyde and an acidic catalyst to obtain polyisobutylene phenyl polyether Mannich base. (4) The polyisobutylene benzene polyether Mannich base obtained in step (3) is reacted with a quaternizing agent to obtain the quaternized Mannich base.

6. The quaternized Mannich base multifunctional fuel additive as described in claim 5, characterized in that: In step (1), the catalyst is at least one selected from boron trifluoride, boron trifluoride diethyl ether, aluminum trichloride, and zirconium tetrachloride; and / or, In step (1), the reaction temperature is 50~130℃, and the reaction time is 2~12h; and / or, In step (2), the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium hydride, and sodium amino; and / or, the molar ratio of the polyisobutylene aromatic phenol and the C2-C4 epoxide is 1:2~10; and / or, In step (2), the reaction temperature is 90~140℃, the reaction time is 1~8h, and the reaction pressure is 0.2~0.4MPa.

7. The quaternized Mannich base multifunctional fuel additive as described in claim 6, characterized in that: In step (1), the molar ratio of the aromatic phenol, polyisobutylene, and catalyst is 1~3:1:0.1~0.6; and / or, In step (2), the amount of alkaline catalyst used is 0.5 to 2% of the mass of the polyisobutylene aromatic phenol.

8. The quaternized Mannich base multifunctional fuel additive as described in claim 5, characterized in that: In step (3), the acidic catalyst is at least one of sulfuric acid, phosphoric acid, and p-toluenesulfonic acid, and the mass amount of the acidic catalyst is 0.2 to 2 times that of the polyisobutylene phenyl polyether; and / or, the molar ratio of the polyisobutylene phenyl polyether, formaldehyde, and N,N'-dimethyl-alkyldiamine is 1:1 to 2:1 to 2; and / or, In step (3), the reaction temperature is 60~130℃, and the reaction time is 3~12h; and / or, In step (4), the molar ratio of the polyisobutylene benzene polyether Mannich base to the quaternizing agent is 1:0.95~1.2; and / or, In step (4), the reaction temperature is 60~130℃ and the reaction time is 4~18h.

9. The quaternized Mannich base multifunctional fuel additive as described in claim 1, characterized in that: Each component is based on 100 parts by weight of solvent oil. 100 parts by weight of solvent oil; 30-40 parts by weight of quaternized Mannich base; 1-10 parts by weight of organometallic compounds; 2-8 parts by weight of acetylenic diol polyether; Antioxidant 0.5 to 2 parts by weight.

10. The quaternized Mannich base multifunctional fuel additive as described in claim 1, characterized in that: 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 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 organometallic compound is at least one of the following: saturated or unsaturated fatty acid iron with 6 to 22 carbon atoms, saturated or unsaturated fatty acid cerium with 6 to 22 carbon atoms, crown ether iron complex, porphyrin iron complex, crown ether platinum complex, porphyrin platinum complex, and ferrocene; and / or, The antioxidant is at least one of phenylenediamine, alkylphenylenediamine, p-tert-butylphenol, and 2,6-di-tert-butyl-p-cresol.

11. The quaternized Mannich base multifunctional fuel additive as described in claim 1, characterized in that: The organometallic compound is at least one of ferric naphthenate and cerium petroleum oxide.

12. A method for preparing a quaternized Mannich base multifunctional fuel additive as described in any one of claims 1-11, comprising mixing components including solvent oil, quaternized Mannich base, organometallic compound, acetylacetonate diol polyether and antioxidant in a specified amount until uniformly mixed to obtain the quaternized Mannich base multifunctional fuel additive.

13. The application of a multifunctional fuel additive as described in any one of claims 1-11 or a multifunctional fuel additive prepared by the method of claim 12 in diesel vehicle fuel, wherein the multifunctional fuel additive is used in a volume ratio of 1 / 10000 to 1 / 10 of the fuel.

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