Fuel oil detergent component as well as preparation method and application thereof

Abstract

The invention discloses a fuel detergent component as well as a preparation method and application thereof. The fuel oil detergent component is a compound shown in a formula (1) or a formula (2): # imgabs0 #, Ra, Rb and Rc are the same or different, are respectively and independently selected from one of phenyl, substituted phenyl, H, NO2 and C1-C20 alkyl, and are preferably selected from one of phenyl, C1-C4 alkoxy substituted phenyl, H and NO2; rd is selected from # imgabs 1 # or # imgabs 2 #; R1 is selected from methyl and / or ethyl; x1 is equal to 0-3, y1 is equal to 2-30, and x1 + y1 is equal to 5-30; preferably, x1 is equal to 1-3, y1 is equal to 5-24, and x1 + y1 is equal to 8-24. The fuel oil clearing agent can efficiently clean fuel oil nozzle carbon deposition, air inlet valve carbon deposition and combustion chamber carbon deposition, porphyrin groups in the fuel oil clearing agent can be complexed with metal ions, combustion characteristics are improved, pollutant emission is reduced, and the comprehensive performance is excellent.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel additives, and in particular to a fuel detergent component and a preparation method and application thereof. Background Art

[0002] In recent years, as countries have become increasingly stringent with their emission standards for automobile pollutants, people's environmental awareness has gradually increased, and more and more car owners are choosing to add fuel detergents.

[0003] Fuel detergents are composite additives with cleaning, dispersing, antioxidant, and rust-preventing properties. They not only inhibit the formation of deposits within the fuel system but also quickly disperse and remove existing deposits, thereby ensuring the proper performance of vehicle engines and improving fuel combustion. Currently, conventional detergents include hydrocarbon-substituted (poly)amine detergents, represented by polyisobutyleneamine; amide (imide) detergents, represented by polyisobutylene succinimide; polyetheramine detergents; and Mannich base detergents. Among them, amide (imide) detergents have excellent cleaning ability for deposits at the fuel injector, but cannot clean deposits at high-temperature components; hydrocarbon-substituted (poly)amine detergents and Mannich base detergents can effectively clean deposits at the fuel injector and intake valve, but will increase combustion chamber deposits; conventional polyetheramine detergents can effectively remove combustion chamber carbon deposits, but they have poor thermal stability and are almost completely decomposed when the temperature exceeds 300°C, so they are not effective in cleaning high-temperature components such as intake valves.

[0004] Therefore, there is a need for a new type of detergent that can not only efficiently remove carbon deposits in the combustion chamber, but also has an excellent cleaning effect on high-temperature components such as the intake valve. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a fuel detergent component, preparation method, and application thereof. This fuel detergent not only effectively cleans carbon deposits on fuel nozzles, intake valves, and combustion chambers, but also features porphyrin groups that complex metal ions, improving combustion characteristics and reducing emissions, resulting in excellent overall performance.

[0006] One of the objects of the present invention is to provide a fuel detergent component, which is a compound represented by the following formula (1) or formula (2):

[0007]

[0008] Among them, R a 、R b 、R c The same or different, each independently selected from phenyl, substituted phenyl, H, NO2, C1-C 20One of the alkyl groups, preferably one selected from phenyl, C1-C4 alkoxy substituted phenyl, H, NO2; R d Selected from * represents the connection position; R 1 Selected from methyl and / or ethyl; x1=0-3, y1=2-30, and x1+y1=5-30; preferably, x1=1-3, y1=5-24, and x1+y1=8-24; more preferably, x1=1-3, y1=12-20, and x1+y1=13-23; x1, y1, x2, y2 represent the average degree of polymerization.

[0009] When R 1 When selected from methyl and ethyl, it means include and and and Random arrangement.

[0010] The structure of the fuel detergent component in the present invention is theoretically deduced from the chemical reaction mechanism and the amount of added raw materials.

[0011] A second object of the present invention is to provide a method for preparing the fuel detergent component of the first object of the present invention, comprising:

[0012] 1) reacting an amino-containing porphyrin with propylene oxide in the presence of an organic solvent and a base catalyst A to obtain a porphyrin intermediate;

[0013] II) reacting the porphyrin intermediate obtained in step I) with butylene oxide and / or propylene oxide in the presence of a base catalyst B to obtain a porphyrin polyether;

[0014] III) introducing liquid ammonia and hydrogen into the porphyrin polyether obtained in step II) in the presence of an amination reaction catalyst to carry out an amination reaction to obtain the fuel detergent component.

[0015] The fuel detergent component of the present invention is preferably characterized by being prepared by the above-mentioned preparation method of the present invention.

[0016] In a preferred embodiment of the present invention,

[0017] In step 1),

[0018] The amino-containing porphyrin has the following structure:

[0019] Among them, R a 、R b 、R c The same or different, each independently selected from phenyl, substituted phenyl, H, NO2, C1-C 20One of the alkyl groups, preferably one selected from phenyl, C1-C4 alkoxy substituted phenyl, H, NO2; R d Selected from * indicates the connection location; and / or,

[0020] The base catalyst A is at least one of potassium hydroxide, sodium hydroxide, sodium ethoxide, and sodium hydride; and / or,

[0021] The organic solvent is at least one of toluene, xylene, trimethylbenzene, ethylbenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and / or

[0022] The molar ratio of propylene oxide to amino-containing porphyrin is (1-4):1, preferably (2-4):1; and / or,

[0023] The mass ratio of the amino-containing porphyrin to the organic solvent is 1:(0.5-5), preferably 1:(0.5-2); and / or,

[0024] The amount of the base catalyst A is 0.2 to 5% of the mass of propylene oxide, preferably 0.2 to 4%; and / or,

[0025] The reaction temperature is 110-140° C., preferably 125-135° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0026] In a preferred embodiment of the present invention,

[0027] In step II),

[0028] The base catalyst B is at least one of potassium hydroxide, sodium hydroxide, sodium ethoxide, and sodium hydride; and / or

[0029] The total molar amount of propylene oxide and butylene oxide in step II) is 2 to 30 times, preferably 5 to 24 times, more preferably 12 to 20 times, the molar amount of the amino-containing porphyrin; and / or

[0030] The amount of the base catalyst B is 0.2 to 5%, preferably 0.2 to 4%, of the total mass of the propylene oxide and butylene oxide introduced in step II); and / or,

[0031] The reaction temperature is 110-140° C., preferably 120-140° C.; preferably, the reaction is stopped when the pressure drops to negative pressure.

[0032] In a preferred embodiment of the present invention,

[0033] In step III),

[0034] The amination reaction catalyst is at least one of Raney nickel catalysts; and / or,

[0035] The amount of the amination reaction catalyst used is 5-20% of the mass of the porphyrin polyether obtained in step II), preferably 5-15%; and / or,

[0036] The amount of liquid ammonia used is 2 to 20 times, preferably 2 to 15 times, the molar amount of porphyrin polyether used; and / or,

[0037] The amount of hydrogen used is 1 to 20 times, preferably 1 to 15 times, the molar amount of porphyrin polyether; and / or,

[0038] The amination reaction temperature is 120-220° C., preferably 150-200° C.; and / or the amination reaction time is 2-12 h, preferably 5-10 h; and / or the amination reaction pressure is 2-10 MPa, preferably 5-10 MPa.

[0039] The preparation method of the fuel detergent component of the present invention can adopt the following specific technical solutions:

[0040] I) placing an amino-containing porphyrin, an organic solvent, and an alkaline catalyst A into an autoclave, evacuating the air, then heating to 110-140° C., introducing propylene oxide in a molar ratio of (1-4):1 to the amino-containing porphyrin to carry out a polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing the heat-insulating reaction after the pressure drops to negative pressure, cooling to below 80° C., neutralizing, dehydrating, filtering, and distilling off the solvent to obtain a porphyrin intermediate;

[0041] II) placing the porphyrin intermediate obtained in step I) and the base catalyst B into an autoclave, evacuating the air, then heating to 110-140° C., introducing butylene oxide and / or propylene oxide in a total molar amount that is 2-30 times the molar amount of the amino-containing porphyrin to carry out a polymerization reaction, controlling the reaction pressure not to exceed 0.3 MPa, and continuing the reaction at the temperature after the pressure drops to negative pressure and then cooling to below 80° C., neutralizing, dehydrating, and filtering the reaction mixture to obtain a porphyrin polyether;

[0042] III) adding the porphyrin polyether obtained in step II) and an amination reaction catalyst to an autoclave, removing air by vacuum, introducing liquid ammonia and hydrogen, and conducting an amination reaction at 2-10 MPa and 120-220° C. for 2-12 hours, followed by cooling to below 80° C., taking out the reaction mixture, filtering to remove insoluble matter, and distilling the filtrate to remove unreacted liquid ammonia, thereby obtaining the fuel detergent component.

[0043] The third object of the present invention is to provide a fuel detergent comprising solvent oil, acetylene glycol polyether and the fuel detergent component of the first object of the present invention or the fuel detergent component obtained by the preparation method of the second object of the present invention; preferably,

[0044] Each component is calculated based on 100 parts by weight of solvent oil.

[0045] The fuel detergent component is 10 to 100 parts by weight; preferably 20 to 80 parts by weight; more preferably 30 to 60 parts by weight;

[0046] 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 2 to 8 parts by weight; more preferably 2 to 4 parts by weight.

[0047] In a preferred embodiment of the present invention,

[0048] The solvent oil is a conventional solvent oil in the prior art, preferably an alkane solvent oil with a boiling range of 60 to 200°C, an aromatic solvent oil with a boiling range of 60 to 200°C, a C6 to C 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,

[0049] The structural formula of the acetylene glycol polyether is as follows:

[0050]

[0051] Wherein, R2 and R3 are methyl groups, 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, n1 and n2 are the same or different, n1+n2=0 to 20, and m1, m2, n1, and n2 are not all 0. (The acetylene glycol polyether is preferably prepared by the method described in Chinese Patent No. 202211702264.2, which is incorporated herein in its entirety.)

[0052] In a preferred embodiment of the present invention,

[0053] The fuel detergent further comprises an antioxidant; preferably,

[0054] The antioxidant is a conventional antioxidant in the prior 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); more preferably, based on 100 parts by weight of solvent oil, the amount of the antioxidant is 0.1 to 2 parts by weight, preferably 0.5 to 2 parts by weight.

[0055] Conventional components in the art, such as other polyethers besides acetylene glycol polyether, may also be added to the formulation of the fuel detergent of the present invention. The amounts used are also conventional amounts and can be adjusted by those skilled in the art according to actual conditions.

[0056] The fourth object of the present invention is to provide a method for preparing the fuel detergent of the third object of the present invention, comprising the step of uniformly mixing the components including the fuel detergent component, solvent oil, acetylene glycol polyether and an optional antioxidant.

[0057] A fifth object of the present invention is to provide a fuel detergent component according to one of the objects of the present invention, or a fuel detergent component obtained by the preparation method according to the second object of the present invention, or a fuel detergent according to the third object of the present invention, or a fuel detergent obtained by the preparation method according to the fourth object of the present invention, and use the same in fuel, preferably in gasoline.

[0058] The present invention has the following beneficial effects:

[0059] The fuel detergent component of the present invention is a polyetheramine containing a porphyrin structural unit. This polyetheramine containing a porphyrin structural unit exhibits higher thermal stability than conventional polyetheramines and excellent dispersibility. Furthermore, compared to conventional polyetheramines, the polyetheramine containing a porphyrin structural unit contains more nitrogen atoms in its structure, making the fuel detergent containing this specific fuel detergent component more efficient in cleaning carbon deposits on fuel nozzles, intake valves, and combustion chambers. Furthermore, the acetylene glycol polyether contained in the fuel detergent of the present invention exhibits low foaming and defoaming properties, making it less prone to foaming during use and allowing for strong adsorption to metal surfaces, inhibiting corrosion of metal surfaces. DETAILED DESCRIPTION

[0060] The present invention will be described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention based on the contents of the present invention still fall within the scope of protection of the present invention.

[0061] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0062] Preparation of decynediol polyoxypropylene (4) ether in Example 1:

[0063] (1) Preparation of nanocatalyst (Mg / Al / Co composite metal oxide catalyst):

[0064] Prepare a mixed solution I of NaOH and Na2CO3 with a molar concentration of 2:1 (the volume of mixed solution I is 100 mL, wherein 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 concentration of 3:1 (the volume of mixed solution II is 100 mL, wherein the molar concentration of Al(NO3)3 is 0.5 mol / L), prepare an equal volume of CoNO3 solution to that of mixed solution II, and its concentration is The molar concentration of Al(NO3)3 in the reaction mixture is 1 / 5; the CoNO3 solution is kept at a constant temperature of 60°C, and the mixed solution I and the mixed solution II are added dropwise thereto simultaneously under vigorous stirring, and the pH value is controlled to be 8.5-9.5 during the addition process; after the addition is completed, the reaction solution is stirred at a constant temperature for 30 minutes, and then placed in a 100°C oven for crystallization for 12 hours; the crystallized slurry is filtered and washed until the filtrate becomes neutral, and the filter cake is placed in an oven for drying; the dried solid is ball-milled in a ball mill to obtain a Mg / Al / Co composite metal oxide catalyst.

[0065] (2) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10, the structural formula of tetramethyldecynediol is: wherein R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2) and 0.9g of the Mg / Al / Co composite metal oxide catalyst obtained in the above step (1) are put into a high-pressure reactor and stirred evenly. The air in the reactor is replaced with nitrogen three times. The high-pressure reactor is evacuated for 30 minutes at 80°C using a vacuum pump, and the evacuation is stopped; 0.8mol of propylene oxide is slowly introduced into the reactor through a feed pipe, and the temperature of the reactor is raised to 115°C. The pressure in the reactor is controlled at about 0.20MPa, and the reaction is stirred for 4 hours; the reaction is stopped after the pressure in the reactor drops to negative pressure, the reaction mixture is taken out, and the nanocatalyst is removed by microporous membrane filtration to obtain decynediol polyoxypropylene (4) ether (TMAD10-PO4); the structural formula of the above decynediol 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.

[0066] Preparation of decynediol polyoxyethylene (8) polyoxypropylene (4) ether in Example 2:

[0067] (1) 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were put into a high-pressure reactor and stirred evenly. The air in the reactor was replaced with nitrogen three times. The high-pressure reactor was evacuated at 80° C. for 30 min using a vacuum pump and the evacuation was stopped. 1.6 mol of ethylene oxide was slowly introduced into the reactor through a feed pipe, and the temperature of the reactor was raised to 115° C. The pressure in the reactor was controlled at about 0.20 MPa and the reaction was stirred for 4 h. The reaction was stopped after the pressure in the reactor dropped to negative pressure, the reaction mixture was taken out, and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxyethylene ether (TMAD10-EO8). The structural formula of the above decynediol polyoxyethylene ether (TMAD10-EO8) is: Wherein, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=0;

[0068] (2) 0.1 mol TMAD10-EO8 and 0.8 g Mg / Al / Co composite metal oxide catalyst were put into a high-pressure reactor and stirred evenly. The air in the reactor was replaced with nitrogen three times. The high-pressure reactor was evacuated at 80° C. for 30 min using a vacuum pump and the evacuation was stopped. 0.4 mol propylene oxide was introduced into the reactor through a feed pipe, and the temperature of the reactor was raised to 125° C. The pressure in the reactor was controlled at about 0.3 MPa and the reaction was stirred for 12 h. The reaction was stopped after the pressure in the reactor dropped to negative pressure. The reaction mixture was taken out and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxyethylene (8) polyoxypropylene (4) ether (TMAD10-EO8-PO4). The structural formula of the above-mentioned acetylene glycol polyoxyethylene polyoxypropylene ether (TMAD10-EO8-PO4) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=8, n1+n2=4.

[0069] Preparation of decynediol polyoxypropylene (8) ether in Example 3:

[0070] 0.2 mol of tetramethyldecynediol (abbreviated as TMAD10) and 0.9 g of the Mg / Al / Co composite metal oxide catalyst obtained above were put into a high-pressure reactor and stirred evenly. The air in the reactor was replaced with nitrogen three times. The high-pressure reactor was evacuated at 80° C. for 30 min using a vacuum pump and the evacuation was stopped. 1.6 mol of propylene oxide was slowly introduced into the reactor through a feed pipe, and the temperature of the reactor was raised to 115° C. The pressure in the reactor was controlled at about 0.20 MPa and the reaction was stirred for 4 h. The reaction was stopped after the pressure in the reactor dropped to negative pressure. The reaction mixture was taken out and the nanocatalyst was removed by microporous membrane filtration to obtain decynediol polyoxypropylene (8) ether (TMAD10-PO8). The structural formula of the above decynediol polyoxypropylene (8) ether (TMAD10-PO8) is: Among them, R2 and R3 are -CH3, R1 and R4 are both -CH2CH(CH3)2, m1+m2=0, n1+n2=8.

[0071] The structure of the acetylene glycol polyether obtained above is theoretically deduced from the reaction mechanism and the added raw materials.

[0072] Example 1

[0073] Preparation of fuel detergent components:

[0074] 1) porphyrin containing an amino group (CAS No.: 294638-98-5, structure ) 1mol, xylene 325mL and potassium hydroxide 4.5g, put into a high-pressure reactor, evacuate to remove air, then heat the reactor to 130°C, pass 116g (2mol) of propylene oxide to carry out polymerization reaction, control the reaction pressure not to exceed 0.3MPa, continue to keep the reaction after completion, wait until the pressure drops to negative pressure and then cool to 80°C, neutralize the reaction mixture with phosphoric acid to pH 7, dehydrate, filter to remove insoluble matter and evaporate the solvent to obtain a porphyrin intermediate;

[0075] II) 1 mol of the above-mentioned porphyrin intermediate and 25 g of potassium hydroxide were placed in an autoclave, and the air was removed by vacuum. The autoclave was then heated to 135° C., 1080 g (15 mol) of butylene oxide was introduced to carry out a polymerization reaction, and the reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the reaction was continued at room temperature. After the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain aminoporphyrin polyoxypropylene polyoxybutylene ether;

[0076] III) 760.5 g of aminoporphyrin polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 85 g of liquid ammonia and 5 mol of hydrogen were introduced, and an amination reaction was carried out at 8 MPa and 180° C. for 8 hours. The reaction mixture was then cooled to 80° C. The reaction mixture was removed and filtered to remove insoluble matter. The unreacted liquid ammonia was evaporated from the filtrate to obtain aminoporphyrin polyoxypropylene polyoxybutylene ether amine-1# (i.e., fuel detergent component-1#).

[0077] Preparation of fuel detergent:

[0078] 100 parts by weight of 60# solvent oil, 50 parts by weight of fuel oil detergent component-1#, 2 parts by weight of decynediol polyoxypropylene (4) ether, and 0.5 parts by weight of p-phenylenediamine were mixed uniformly at 50° C. to obtain fuel oil detergent i#.

[0079] Example 2

[0080] The amino-containing porphyrin used in Example 2 (structural formula is Among them, R a 、R b 、R c All are phenyl, R d for ) was prepared with reference to the literature “Synthesis of New Amino-Functionalized Porphyrins: Preliminary Study of Their Organophotocatalytic Activity, molecules, 2023, 28(4), 1997”.

[0081] Preparation of fuel detergent components:

[0082] I) 1 mol of the above-mentioned amino-containing porphyrin, 250 mL of dimethyl sulfoxide and 3.0 g of potassium hydroxide were put into an autoclave, and the air was removed by evacuation. The reactor was then heated to 130° C., 174 g (3 mol) of propylene oxide was introduced to carry out polymerization, and the reaction pressure was controlled to be no more than 0.3 MPa. After the reaction was completed, the reaction was continued at a temperature of 80° C. after the pressure dropped to a negative pressure. The reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, filtered to remove insoluble matter, and the solvent was evaporated to obtain a porphyrin intermediate;

[0083] II) 1 mol of the above-mentioned porphyrin intermediate and 20.0 g of potassium hydroxide were placed in an autoclave, and the air was removed by vacuum. The reactor was then heated to 130° C., 1044 g (18 mol) of propylene oxide was introduced to carry out polymerization reaction, and the reaction pressure was controlled not to exceed 0.3 MPa. After the propylene oxide was passed through, the reaction was continued at a temperature of 80° C. after the pressure dropped to a negative pressure. The reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain aminoporphyrin polyoxypropylene ether;

[0084] III) 785.5 g of the aforementioned aminoporphyrin polyoxypropylene ether and 60 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 90 g of liquid ammonia and 5 mol of hydrogen were introduced, and an amination reaction was carried out at 6 MPa and 160° C. for 6 h. The reaction mixture was then cooled to 80° C. The reaction mixture was removed and filtered to remove insoluble matter. The unreacted liquid ammonia was evaporated from the filtrate to obtain aminoporphyrin polyoxypropylene ether amine-2# (i.e., fuel detergent component-2#).

[0085] Preparation of fuel detergent:

[0086] Mix 100 parts by weight of 80# solvent oil, 35 parts by weight of fuel detergent component-2#, 2 parts by weight of decynediol polyoxyethylene (8) polyoxypropylene (4) ether, and 0.5 parts by weight of p-tert-butylphenol at 50°C to obtain fuel detergent ii#.

[0087] Example 3

[0088] Preparation of fuel detergent components:

[0089] 1) porphyrin containing an amino group (CAS No.: 294638-98-5, structure ) 1mol, 325mL of xylene and 4.5g of potassium hydroxide were put into a high-pressure reactor, and the air was removed by vacuum. Then the reactor was heated to 130°C, and 174g (3mol) of propylene oxide was introduced to carry out polymerization reaction. The reaction pressure was controlled not to exceed 0.3MPa. After the reaction was completed, the reaction was continued at room temperature. After the pressure dropped to negative pressure, the temperature was lowered to 80°C. The reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, filtered to remove insoluble matter, and the solvent was evaporated to obtain a porphyrin intermediate;

[0090] II) 1 mol of the above-mentioned porphyrin intermediate and 30 g of potassium hydroxide were put into an autoclave, and the air was removed by vacuum. The reactor was then heated to 130° C., 1080 g (15 mol) of butylene oxide and 290 g (5 mol) of propylene oxide were introduced to carry out a polymerization reaction, and the reaction pressure was controlled not to exceed 0.3 MPa. After the reaction was completed, the reaction was continued at room temperature. After the pressure dropped to negative pressure, the temperature was lowered to 80° C., and the reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain aminoporphyrin polyoxypropylene polyoxybutylene ether;

[0091] III) 934.5 g of aminoporphyrin polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reaction kettle, and the air in the kettle was removed by vacuum. 90 g of liquid ammonia and 6 mol of hydrogen were introduced, and an amination reaction was carried out at 9 MPa and 190° C. for 8 hours. The reaction mixture was then cooled to 80° C. The reaction mixture was removed and filtered to remove insoluble matter. The unreacted liquid ammonia was evaporated from the filtrate to obtain aminoporphyrin polyoxypropylene polyoxybutylene ether amine-3# (i.e., fuel detergent component-3#).

[0092] Preparation of fuel detergent:

[0093] Mix 100 parts by weight of 100# solvent oil, 50 parts by weight of fuel oil detergent component-3#, 2 parts by weight of decynediol polyoxypropylene (8) ether, and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol at 50° C. to obtain fuel oil detergent iii#.

[0094] Comparative Example 1

[0095] Preparation of polyoxypropylene polyoxybutylene ether amine:

[0096] (1) 76 g (1 mol) of 1,2-propylene glycol and 15 g of potassium hydroxide were placed in a high-pressure reactor, and the air was removed by vacuum. The reactor was then heated to 125° C., 406 g (7 mol) of propylene oxide was first introduced to carry out polymerization reaction, and then 1080 g (15 mol) of butylene oxide was introduced to carry out 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. The reaction mixture was neutralized with phosphoric acid to a pH of 7, dehydrated, and filtered to remove insoluble matter to obtain polyoxypropylene polyoxybutylene ether;

[0097] (2) 781 g of polyoxypropylene polyoxybutylene ether and 50 g of Raney nickel catalyst (CAS No. 7440-02-0) were placed in a reactor, and the air in the reactor was removed by vacuum. 90 g of liquid ammonia and 6 mol of hydrogen were introduced, and an amination reaction was carried out at 9 MPa and 190° C. for 8 h. The reaction mixture was then cooled to 80° C., and the insoluble matter was removed by filtration. The unreacted liquid ammonia was removed from the filtrate to obtain polyoxypropylene polyoxybutylene ether amine.

[0098] Preparation of fuel detergent:

[0099] Mix 100 parts by weight of 100# solvent oil, 50 parts by weight of polyoxypropylene polyoxybutylene ether amine, 2 parts by weight of decynediol polyoxypropylene (8) ether (same as in Example 3), and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol at 50° C. to obtain fuel detergent IV#.

[0100] Comparative Example 2

[0101] Preparation of fuel detergent:

[0102] 100 parts by weight of 100# solvent oil, porphyrin containing amino group (CAS No.: 294638-98-5, structure: ), 16 parts by weight of polyoxypropylene polyoxybutylene ether amine prepared in Comparative Example 1, 34 parts by weight of decynediol polyoxypropylene (8) ether (same as in Example 3), and 0.5 parts by weight of 2,6-di-tert-butyl-p-cresol are mixed uniformly at 50°C to obtain fuel detergent v#.

[0103] Comparative Example 3

[0104] Preparation of fuel detergent:

[0105] 100 parts by weight of 60# solvent oil, 50 parts by weight of polyetheramine D2000, 2 parts by weight of decynediol polyoxypropylene (4) ether (same as in Example 1), and 0.5 parts by weight of p-phenylenediamine were mixed uniformly at 50° C. to obtain fuel oil detergent vi#.

[0106] Test Case

[0107] The same concentration (recommended ratio: 800 mg / L (calculated as polyetheramine)) of a commercially available gasoline detergent, as well as the fuel detergents of Examples 1 to 3 and Comparative Examples 1 to 3, was added to 92# base gasoline. Carbon deposit removal data were compared according to the method of GB / T 19230.6. The data comparison is shown in Table 1 below.

[0108] Table 1 Performance comparison of gasoline additives in Examples and Comparative Examples

[0109]

[0110]

[0111] As can be seen from Example 3, Comparative Examples 1-2, and Table 1, the fuel detergent containing the porphyrin polyetheramine of the present invention exhibits significantly superior cleaning effects on the fuel intake system and combustion chamber of automobile engines compared to the addition of a polyetheramine prepared under the same conditions as the present invention using a conventional initiator (e.g., propylene glycol) to the fuel detergent (Comparative Example 1) or the further addition of an amino-containing porphyrin (Comparative Example 2). As can be seen from Example 1, Comparative Example 3, and Table 1, the fuel detergent containing the porphyrin polyetheramine of the present invention exhibits significantly superior cleaning effects on the fuel intake system and combustion chamber of automobile engines compared to conventional polyetheramines used in the prior art.

[0112] As can be seen from Examples 1-3 and Table 1, the fuel detergent of the present invention, when added to commercially available automotive gasoline, has a significant cleaning effect on the fuel intake system and combustion chamber of an automobile engine. This allows the engine to maintain excellent operating conditions over a long period of time, prevents excessive increases in fuel consumption, and reduces harmful exhaust emissions, thereby reducing engine maintenance costs and extending engine service life.

Claims

1. A fuel detergent component, which is a compound represented by the following formula (1) or formula (2): in, R a 、R b 、R c The same or different, each independently selected from phenyl, substituted phenyl, H, NO2, C1-C 20 One of the alkyl groups, preferably one selected from phenyl, C1-C4 alkoxy substituted phenyl, H, NO2; R d Selected from R 1 Selected from methyl and / or ethyl; x1=0-3, y1=2-30, and x1+y1=5-30; preferably, x1=1-3, y1=5-24, and x1+y1=8-24.

2. A method for preparing the fuel detergent component according to claim 1, comprising: 1) reacting an amino-containing porphyrin with propylene oxide in the presence of an organic solvent and a base catalyst A to obtain a porphyrin intermediate; II) reacting the porphyrin intermediate obtained in step I) with butylene oxide and / or propylene oxide in the presence of a base catalyst B to obtain a porphyrin polyether; III) introducing liquid ammonia and hydrogen into the porphyrin polyether obtained in step II) in the presence of an amination reaction catalyst to carry out an amination reaction to obtain the fuel detergent component.

3. The preparation method according to claim 2, wherein: In step 1), The amino-containing porphyrin has the following structure: Among them, R a 、R b 、R c The same or different, each independently selected from phenyl, substituted phenyl, H, NO2, C1-C 20 One of the alkyl groups, preferably one selected from phenyl, C1-C4 alkoxy substituted phenyl, H, NO2; R d Selected from and / or, The base catalyst A is at least one of potassium hydroxide, sodium hydroxide, sodium ethoxide, and sodium hydride; and / or, The organic solvent is at least one of toluene, xylene, trimethylbenzene, ethylbenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and / or The molar ratio of propylene oxide to amino-containing porphyrin is (1-4):1, preferably (2-4):1; and / or, The mass ratio of the amino-containing porphyrin to the organic solvent is 1:(0.5-5), preferably 1:(0.5-2); and / or, The amount of the base catalyst A is 0.2 to 5% of the mass of propylene oxide, preferably 0.2 to 4%; and / or, The reaction temperature is 110-140°C, preferably 125-135°C.

4. The preparation method according to claim 2, wherein: In step II), The base catalyst B is at least one of potassium hydroxide, sodium hydroxide, sodium ethoxide, and sodium hydride; and / or The total molar amount of propylene oxide and butylene oxide in step II) is 2 to 30 times, preferably 5 to 24 times, the molar amount of the amino-containing porphyrin; and / or, The amount of the base catalyst B is 0.2 to 5%, preferably 0.2 to 4%, of the total mass of the propylene oxide and butylene oxide introduced in step II); and / or, The reaction temperature is 110-140°C, preferably 120-140°C.

5. The preparation method according to claim 2, wherein: In step III), The amination reaction catalyst is at least one of Raney nickel catalysts; and / or, The amount of the amination reaction catalyst used is 5-20% of the mass of the porphyrin polyether obtained in step II), preferably 5-15%; and / or, The amount of liquid ammonia used is 2 to 20 times, preferably 2 to 15 times, the molar amount of porphyrin polyether used; and / or, The amount of hydrogen used is 1 to 20 times, preferably 1 to 15 times, the molar amount of porphyrin polyether; and / or, The amination reaction temperature is 120-220° C., preferably 150-200° C.; and / or the amination reaction time is 2-12 h, preferably 5-10 h; and / or the amination reaction pressure is 2-10 MPa, preferably 5-10 MPa.

6. A fuel detergent comprising solvent oil, acetylene glycol polyether and the fuel detergent component according to claim 1 or the fuel detergent component prepared by the method according to any one of claims 2 to 5; preferably, Each component is calculated based on 100 parts by weight of solvent oil. The fuel detergent component is 10 to 100 parts by weight, preferably 20 to 80 parts by weight; 0.5 to 10 parts by weight of acetylene glycol polyether; preferably 2 to 8 parts by weight.

7. The fuel detergent according to claim 6, characterized in that: The solvent oil is an alkane solvent oil with a boiling range of 60 to 200°C, an aromatic solvent oil with a boiling range of 60 to 200°C, a C6 to C 12 At least one of alkyl alcohols; and / or The structural formula of the acetylene glycol polyether is as follows: Wherein, R2 and R3 are methyl groups, 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, n1 and n2 are the same or different, n1+n2=0 to 20, and m1, m2, n1, and n2 are not 0 at the same time.

8. The fuel detergent according to claim 6, characterized in that: The fuel detergent further comprises an antioxidant; preferably, The antioxidant is 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).

9. A method for preparing the fuel detergent according to any one of claims 6 to 8, comprising the step of uniformly mixing components including the fuel detergent component, solvent oil, acetylene glycol polyether and an optional antioxidant.

10. Use of the fuel detergent component according to claim 1, or the fuel detergent component obtained by the preparation method according to any one of claims 2 to 5, or the fuel detergent according to any one of claims 6 to 8, or the fuel detergent obtained by the preparation method according to claim 9 in fuel, preferably in gasoline.

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