CN110484312B - Gasoline detergent and preparation method thereof - Google Patents

Gasoline detergent and preparation method thereof Download PDF

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CN110484312B
CN110484312B CN201910837049.5A CN201910837049A CN110484312B CN 110484312 B CN110484312 B CN 110484312B CN 201910837049 A CN201910837049 A CN 201910837049A CN 110484312 B CN110484312 B CN 110484312B
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component
parts
formula
gasoline
mannich base
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CN110484312A (en
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崔卫华
马雪菲
张超
梁万根
杨聪
宋吻吻
崔振杰
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Shandong Jingbo Zhongcheng Clean Energy Co ltd
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Shandong Efirm Biochemistry and Environmental Protection Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
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    • C10L1/18—Organic compounds containing oxygen
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/188—Carboxylic acids; metal salts thereof
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
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    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
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    • C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas

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  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention provides a gasoline detergent which comprises the following components: 15-35 parts by weight of Mannich base; 3-8 parts of a demulsifying component; 10-20 parts of octane number promoting component; 5-12 parts of antioxidant component; 0.5 to 2 parts by weight of a corrosion inhibiting component; 30-60 parts of solvent oil; the Mannich base has a structure represented by formula (1); in the formula (I), R1Is composed of

Description

Gasoline detergent and preparation method thereof
Technical Field
The invention relates to the technical field of engine detergents, in particular to a gasoline detergent and a preparation method thereof.
Background
In recent years, people pay more and more attention to the treatment of automobile exhaust under the pressure of environmental protection and energy conservation. In order to increase the rotation speed and power of the engine, reduce pollution and save fuel, the foreign automobile companies pay attention to accurately control the fuel-air ratio in the design of the combustion system so as to fully combust the fuel, and a hole type fuel injector is adopted to replace a carburetor. The popularization and the application of the technology are a great breakthrough of the energy-saving and environment-friendly technology, but certain problems are brought, the requirement on the nozzle is very strict due to the strict control of the air fuel ratio, and the nozzle is easy to block by using common lead-free gasoline. In order to solve the problem, the development and use of gasoline detergents are started abroad, and the gasoline detergents are required to be added into high-quality gasoline specified in Japan and America. China also moves with the trend of times, the national environmental protection Bureau 1999 issues a requirement that 'a detergent capable of effectively removing carbon deposition should be added to the gasoline for automobiles', the national standard of 'unleaded gasoline' promulgated and implemented in 2000 of China stipulates that from 7 months and 1 days in 2000, gasoline sold in Beijing, Shanghai and Guangzhou markets must be added with a gasoline detergent. In addition, in the aspect of environmental protection, after the gasoline detergent is added, the contents of CO and HC in automobile exhaust are greatly reduced, great benefits are provided for improving urban environmental pollution and improving the quality of life of people, and meanwhile, the gasoline detergent plays a positive role in guaranteeing that the emission of strict banning executed by traffic management and environmental protection departments exceeds the standard of automobile on-road running.
At present, the commercial gasoline detergent has various varieties and various performances, and has the following technical problems: (1) the main agent can not be decomposed in the combustion chamber, so that the deposit in the combustion chamber is increased; (2) the emulsification of the oil product is easy to cause, and the demulsification property of the oil product is reduced; (3) the universality is poor, and the complex gasoline component change and the requirements of gasoline with different grades of 92, 95, 98 and higher octane numbers are difficult to deal with.
Disclosure of Invention
In view of the above, the invention aims to provide a gasoline detergent and a preparation method thereof, and the gasoline detergent provided by the invention has the advantages that the decomposition temperature of a main agent is low, the sediments of an air inlet valve and an oil nozzle can be better cleaned, the sediments of a combustion chamber are not increased, the oil emulsification is not easy to cause, the requirements of gasolines of different types and components can be met, and the universality is strong.
The invention provides a gasoline detergent which comprises the following components:
15-35 parts by weight of Mannich base;
3-8 parts of a demulsifying component;
10-20 parts of octane number promoting component;
5-12 parts of antioxidant component;
0.5 to 2 parts by weight of a corrosion inhibiting component;
30-60 parts of solvent oil;
the Mannich base has the structure shown in formula (I):
Figure GDA0003058132050000021
in the formula (I), R1Is composed of
Figure GDA0003058132050000022
Wherein n is 8-12; and m is 5-10.
Preferably, the preparation method of the Mannich base comprises the following steps:
a) mixing phenol and high-activity polyisobutylene in a solvent, and carrying out a first reaction in the presence of a first catalyst to obtain polyisobutylene phenol with a structure shown in a formula (II);
Figure GDA0003058132050000023
in the formula (II), R1Is composed of
Figure GDA0003058132050000031
Wherein n is 8-12;
b) mixing the polyisobutylene phenol obtained in the step a) and ethylene oxide according to a molar ratio of 1: (5-10), and carrying out a second reaction in the presence of a second catalyst to obtain p-polyisobutenyl polyoxyethylene ether with a structure shown in a formula (III);
Figure GDA0003058132050000032
in the formula (III), R1Is composed of
Figure GDA0003058132050000033
Wherein n is 8-12; m is 5-10;
c) mixing the p-polyisobutenyl polyoxyethylene ether obtained in the step b), diethylenetriamine and paraformaldehyde in a solvent, and carrying out a third reaction in the presence of a third catalyst to obtain the Mannich base with the structure shown in the formula (I).
Preferably, the temperature of the second reaction in the step b) is 200-280 ℃, the pressure is 0.5-1 MPa, and the time is 2-4 h.
Preferably, the demulsifying component is prepared from the following components in a mass ratio of 10: (3-8): (30-40): (40-50) isooctyl alcohol, isoamyl alcohol, N-diethylhydroxylamine and lauryl alcohol polyoxyethylene ether.
Preferably, the octane boosting component is selected from one or more of dimethyl carbonate, polyisobutylene succinimide, and polyisobutylene succinimide.
Preferably, the antioxidant component is one or more selected from 2, 6-di-tert-butylphenol, a T511 antioxidant, a T531 antioxidant and benzotriazole.
Preferably, the corrosion inhibiting component is selected from one or more of imidazoline polyoxypropylene ether, N-benzylpyridine, and tetradecenyl succinic acid.
Preferably, the solvent oil is selected from dearomatized solvent oil and/or white oil.
The invention also provides a preparation method of the gasoline detergent in the technical scheme, which comprises the following steps:
the Mannich base, the demulsifying component, the octane number improving component, the antioxidant component, the corrosion inhibiting component and the solvent oil are uniformly mixed to obtain the gasoline detergent.
Preferably, the mixing mode is stirring; the stirring temperature is 30-60 ℃.
The invention provides a gasoline detergent which comprises the following components: 15-35 parts by weight of Mannich base; 3-8 parts of a demulsifying component; 10-20 parts of octane number promoting component; 5-12 parts of antioxidant component; 0.5 to 2 parts by weight of a corrosion inhibiting component; 30-60 parts of solvent oil; the Mannich base has a structure shown in formula (I); in the formula (I), R1Is composed of
Figure GDA0003058132050000041
Wherein n is 8-12; and m is 5-10. Compared with the prior art, the gasoline detergent provided by the invention takes Mannich base with a specific structure as a main agent, has low decomposition temperature, is not decomposed in an air intake system, can better clean deposits of an air intake valve and an oil nozzle, can be decomposed into micromolecular components after fuel reaches a combustion chamber, is combusted along with the fuel, and does not additionally increase deposits in the combustion chamber; the gasoline can realize better interaction with other components with specific contents, is not easy to cause oil emulsification, can meet the requirements of gasolines with different types and different components, and has strong universality; the product can be used in the vehicle fuel oil to inhibit the generation of fuel oil system deposits, disperse and remove the generated oxidized deposits, ensure the normal exertion of the dynamic property of the vehicle, improve the combustion performance of the fuel oil, further reduce the emission of pollutants and save the oil consumption.
In addition, the preparation method provided by the invention is simple in process, mild in condition, suitable for large-scale industrial production and wide in application prospect.
Drawings
FIG. 1 shows the results of the intake valve deposit test in the M111 bench test machine;
FIG. 2 is the results of an incremental deposit test for the combustion chamber of the M111 bench test machine;
FIG. 3 shows nozzle air flow loss detection results;
FIG. 4 shows the net power test results of GB/T18297-2001 automobile engine Performance test method;
FIG. 5 shows the fuel consumption test results;
FIG. 6 shows HC emission detection results of the entire vehicle;
FIG. 7 shows the results of CO emission measurements for the entire vehicle;
FIG. 8 shows the detergency results of the gasoline detergent of the present invention on three major components of commercial product oil.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a gasoline detergent which comprises the following components:
15-35 parts by weight of Mannich base;
3-8 parts of a demulsifying component;
10-20 parts of octane number promoting component;
5-12 parts of antioxidant component;
0.5 to 2 parts by weight of a corrosion inhibiting component;
30-60 parts of solvent oil;
the Mannich base has the structure shown in formula (I):
Figure GDA0003058132050000051
in the formula (I), R1Is composed of
Figure GDA0003058132050000052
Wherein n is 8-12; and m is 5-10.
In the present invention, the gasoline detergent is preferably composed of a mannich base, a demulsifying component, an octane number boosting component, an antioxidant component, a corrosion inhibiting component, and a solvent oil; wherein, Mannich base is used as a main agent. In the present invention, the Mannich base has the structure of formula (I):
Figure GDA0003058132050000053
in the formula (I), R1Is composed of
Figure GDA0003058132050000061
Wherein n is 8-12; and m is 5-10.
Compared with the Mannich base widely applied to the market, the Mannich base has the advantages that the polyoxyethylene ether block is added, the block polyether has good cleaning dispersibility, colloid, asphaltene and carbon blue components formed by high-temperature oil gas under the action of oxygen can be better dispersed, the components are prevented from being coalesced on an oil nozzle and the inner wall of an engine, the injection path and the injection direction of the oil nozzle are changed, the volume of the engine is reduced, the compression ratio is changed, and the fuel utilization rate is reduced; and the Mannich base has low decomposition temperature, can be decomposed in the combustion chamber after entering the combustion chamber along with fuel oil, and can be combusted along with the fuel oil without increasing the deposit in the combustion chamber.
In the present invention, the preparation method of the mannich base is preferably specifically as follows:
a) mixing phenol and high-activity polyisobutylene in a solvent, and carrying out a first reaction in the presence of a first catalyst to obtain polyisobutylene phenol with a structure shown in a formula (II);
Figure GDA0003058132050000062
in the formula (II), R1Is composed of
Figure GDA0003058132050000063
Wherein n is 8-12;
b) mixing the polyisobutylene phenol obtained in the step a) and ethylene oxide according to a molar ratio of 1: (5-10), and carrying out a second reaction in the presence of a second catalyst to obtain p-polyisobutenyl polyoxyethylene ether with a structure shown in a formula (III);
Figure GDA0003058132050000064
in the formula (III), R1Is composed of
Figure GDA0003058132050000071
Wherein n is 8-12; m is 5-10;
c) mixing the p-polyisobutenyl polyoxyethylene ether obtained in the step b), diethylenetriamine and paraformaldehyde in a solvent, and carrying out a third reaction in the presence of a third catalyst to obtain the Mannich base with the structure shown in the formula (I).
The invention firstly mixes phenol and high-activity polyisobutylene in a solvent, and carries out a first reaction in the presence of a first catalyst to obtain the polyisobutylene phenol with the structure shown in the formula (II). The present invention is not particularly limited in kind and source of the solvent, and toluene well known to those skilled in the art may be used. In the present invention, the first catalyst is preferably boron trifluoride. In the present invention, the amount ratio of the phenol, the high-activity polyisobutylene, the solvent and the first catalyst is preferably 0.1 mol: (30 mL-50 mL): 0.05 mol: (0.01mol to 0.02mol), more preferably 0.1 mol: 40mL of: 0.05 mol: 0.015 mol.
The mixing apparatus of the present invention is not particularly limited, and a four-necked flask equipped with a stirrer, a condenser, a separatory funnel and a thermometer, which are well known to those skilled in the art, may be used. In the present invention, the process of mixing phenol and high-activity polyisobutylene in a solvent and carrying out the first reaction in the presence of the first catalyst is preferably embodied as follows:
adding phenol, a solvent and a first catalyst into a four-neck flask, and installing a stirrer, a condenser tube, a separating funnel and a thermometer on the four-neck flask; dissolving high-activity polyisobutylene in a solvent, placing the solvent in a separating funnel, introducing nitrogen to keep normal pressure, controlling the temperature to be the first reaction temperature, and then dropwise adding the high-activity polyisobutylene in the separating funnel for carrying out the first reaction. In the present invention, the temperature of the first reaction is preferably 70 ℃ to 90 ℃, more preferably 80 ℃; the time for the first reaction is preferably 2 to 4 hours, and more preferably 3 hours.
After the first reaction is completed, the present invention preferably further comprises:
and (3) carrying out primary post-treatment on the product after the primary reaction to obtain the polyisobutene phenol with the structure shown in the formula (II). In the present invention, the first post-treatment process preferably includes:
and (3) after the reaction is finished, standing, taking out an organic layer until the catalyst is completely deposited to the bottom of the four-neck flask, washing with hot water for 3-5 times to remove unreacted phenol and the catalyst, standing and cooling, performing suction filtration to remove insoluble substances, and performing reduced pressure distillation on filtrate to remove the solvent and unreacted small molecular substances to obtain the polyisobutene phenol with the structure shown in the formula (II).
After obtaining the polyisobutylene phenol, the invention enables the obtained polyisobutylene phenol and the ethylene oxide to be mixed according to a molar ratio of 1: (5-10), and carrying out a second reaction in the presence of a second catalyst to obtain the p-polyisobutenyl polyoxyethylene ether with the structure shown in the formula (III). In the present invention, the second catalyst is preferably raney nickel; the amount of the catalyst is preferably 4 to 6 percent, more preferably 5 percent of the total mass of the polyisobutylene phenol and the ethylene oxide.
The apparatus for mixing according to the present invention is not particularly limited, and a high-pressure reactor known to those skilled in the art may be used.
In the present invention, the temperature of the second reaction is preferably 200 to 280 ℃, more preferably 220 ℃; the pressure of the second reaction is preferably 0.5MPa to 1MPa, and more preferably 0.5 MPa; the time of the second reaction is preferably 2 to 4 hours, and more preferably 3 hours.
After the second reaction is completed, the present invention preferably further comprises:
and (3) carrying out secondary post-treatment on the product obtained after the secondary reaction to obtain the p-polyisobutenyl polyoxyethylene ether with the structure shown in the formula (III). In the present invention, the second post-treatment process preferably includes:
after the reaction is finished, cooling to 50-70 ℃, filtering to remove insoluble substances, and distilling the filtrate under reduced pressure to obtain the p-polyisobutenyl polyoxyethylene ether with the structure shown in the formula (III).
After the p-polyisobutenyl polyoxyethylene ether is obtained, the obtained p-polyisobutenyl polyoxyethylene ether, diethylenetriamine and paraformaldehyde are mixed in a solvent, and a third reaction is carried out in the presence of a third catalyst to obtain the Mannich base with the structure shown in the formula (I). The present invention is not particularly limited in kind and source of the solvent, and toluene well known to those skilled in the art may be used. In the present invention, the third catalyst is preferably p-toluenesulfonic acid. In the present invention, the ratio of the amount of the polyisobutenyl polyoxyethylene ether, the solvent and the third catalyst is preferably 0.1 mol: (50 mL-70 mL): (0.1g to 0.3g), more preferably 0.1 mol: 60mL of: 0.2 g.
The mixing apparatus of the present invention is not particularly limited, and a four-necked flask equipped with a stirrer, a condenser, a separatory funnel and a thermometer, which are well known to those skilled in the art, may be used. In the present invention, the preferable process of mixing the obtained p-polyisobutenyl polyoxyethylene ether, diethylenetriamine and paraformaldehyde in a solvent and performing a third reaction in the presence of a third catalyst is specifically:
adding the p-polyisobutenyl polyoxyethylene ether and the solvent into the four-mouth bottle, adding the third catalyst, starting heating and stirring, adding diethylenetriamine into the four-mouth bottle when the temperature rises to the third reaction temperature, introducing nitrogen to keep the normal pressure, rapidly adding paraformaldehyde in batches, continuously heating to the third reaction temperature, keeping the temperature for reaction, and ending the reaction until no water is generated in the water separator. In the present invention, the third reaction temperature is preferably 50 to 70 ℃, more preferably 60 ℃.
After the third reaction is completed, the present invention preferably further comprises:
and (3) carrying out third post-treatment on the product obtained after the third reaction to obtain the Mannich base with the structure shown in the formula (I). In the present invention, the third post-treatment process preferably includes:
after the reaction is finished, cooling the reaction mixture in the four-mouth bottle to 50-70 ℃, filtering to remove insoluble substances, and distilling the filtrate under reduced pressure to obtain the Mannich base with the structure shown in the formula (I).
In the present invention, the gasoline detergent comprises 15 to 35 parts by weight of a mannich base.
In the present invention, the demulsifying component is preferably prepared by mixing, by mass, 10: (3-8): (30-40): (40-50) isooctyl alcohol, isoamyl alcohol, N-diethylhydroxylamine and lauryl polyoxyethylene ether, and the mass ratio is more preferably 10: 5: 35: 45 of isooctyl alcohol, isoamyl alcohol, N-diethylhydroxylamine and lauryl alcohol polyoxyethylene ether. The demulsifying component of the present invention is not particularly limited to isooctanol, isoamyl alcohol, N-diethylhydroxylamine and lauryl polyoxyethylene ether, and commercially available products well known to those skilled in the art can be used. The demulsifying component compounded by the polyether, the amine and the low molecular alcohol has better interaction with other components in the gasoline detergent, so that the demulsifying performance of the additivated gasoline is not reduced, and the problem that the gasoline containing trace moisture is easy to emulsify in the transportation and shaking process is solved (the gasoline detergent in the prior art is easy to emulsify the oil product, the demulsifying performance of the oil product is reduced, and meanwhile, the oil product is easy to emulsify and the oil sample is turbid due to shaking in the transportation process when the oil product contains water). In the present invention, the gasoline detergent includes 3 to 8 parts by weight of a demulsifying component, preferably 4 to 7 parts by weight.
In the present invention, the octane boosting component is preferably selected from one or more of dimethyl carbonate, polyisobutylene succinimide and polyisobutylene succinimide, more preferably dimethyl carbonate, polyisobutylene succinimide or polyisobutylene succinimide. The source of the octane boosting component is not particularly limited in the present invention, and commercially available products of the above-mentioned dimethyl carbonate, polyisobutylene succinimide, and polyisobutylene succinimide, which are well known to those skilled in the art, may be used. In the present invention, the gasoline detergent includes 10 to 20 parts by weight of the octane number boosting component, preferably 12 to 18 parts by weight.
In the present invention, the antioxidant component is preferably selected from one or more of 2, 6-di-tert-butylphenol, T511 antioxidant, T531 antioxidant and benzotriazole, and more preferably 2, 6-di-tert-butylphenol, T511 antioxidant or benzotriazole. The source of the antioxidant component is not particularly limited, and commercially available products of the 2, 6-di-tert-butylphenol, the T511 antioxidant, the T531 antioxidant and the benzotriazole, which are well known to those skilled in the art, can be adopted. In the present invention, the gasoline detergent includes 5 to 12 parts by weight of an antioxidant component, preferably 6 to 12 parts by weight.
In the present invention, the corrosion-inhibiting component is preferably selected from one or more of imidazoline polyoxypropylene ether, N-benzylpyridine, and tetradecenyl succinic acid, and more preferably imidazoline polyoxypropylene ether, N-benzylpyridine, or tetradecenyl succinic acid. The source of the corrosion inhibiting component is not particularly limited in the present invention, and commercially available products of the above imidazoline polyoxypropylene ether, N-benzylpyridine, and tetradecenyl succinic acid, which are well known to those skilled in the art, may be used. In the present invention, the gasoline detergent includes 0.5 to 2 parts by weight of the corrosion inhibiting component, preferably 0.6 to 1.5 parts by weight.
In the present invention, the mineral spirits are preferably selected from dearomatized mineral spirits and/or white oils, more preferably dearomatized mineral spirits or white oils. The source of the solvent oil is not particularly limited in the present invention, and commercially available products of the above-mentioned dearomatized solvent oil and white oil, which are well known to those skilled in the art, may be used. In the present invention, the gasoline detergent includes 30 to 60 parts by weight of the mineral spirit, preferably 36.4 to 55 parts by weight.
The gasoline detergent provided by the invention takes Mannich base with a specific structure as a main agent, has low decomposition temperature, is not decomposed in an air inlet system, can better clean deposits of an air inlet valve and an oil nozzle, can be decomposed into small molecular components after fuel reaches a combustion chamber, burns together with the fuel, and does not additionally increase deposits in the combustion chamber; the gasoline can realize better interaction with other components with specific contents, is not easy to cause oil emulsification, can meet the requirements of gasolines with different types and different components, and has strong universality; the product can be used in the vehicle fuel oil to inhibit the generation of fuel oil system sediments, clean the sediments formed by the engine (disperse and clean the generated oxidized sediments), ensure the normal exertion of the dynamic performance of the vehicle, improve the combustion performance of the fuel oil, further reduce the emission of pollutants, save the oil consumption, and meet the requirements of environmental protection, emission reduction and engine optimization upgrading at the present stage.
The invention also provides a preparation method of the gasoline detergent in the technical scheme, which comprises the following steps:
the Mannich base, the demulsifying component, the octane number improving component, the antioxidant component, the corrosion inhibiting component and the solvent oil are uniformly mixed to obtain the gasoline detergent.
The Mannich base, the demulsifying component, the octane number improving component, the antioxidant component, the corrosion inhibiting component and the solvent oil are uniformly mixed to obtain the gasoline detergent. In the present invention, the mannich base, the demulsifying component, the octane number enhancing component, the antioxidant component, the corrosion inhibiting component and the solvent oil are the same as those described in the above technical scheme, and are not described herein again.
The mixing apparatus of the present invention is not particularly limited, and a reaction vessel known to those skilled in the art may be used. In the present invention, the mixing is preferably performed by stirring; the stirring temperature is preferably 30 to 60 ℃, more preferably 50 ℃.
The preparation method provided by the invention is simple in process, mild in condition, suitable for large-scale industrial production and wide in application prospect.
The invention provides a gasoline detergent which comprises the following components: 15-35 parts by weight of Mannich base; 3-8 parts of a demulsifying component; 10-20 parts of octane number promoting component; 5-12 parts of antioxidant component; 0.5 to 2 parts by weight of a corrosion inhibiting component; 30-60 parts of solvent oil; the Mannich base has a structure shown in formula (I); in the formula (I)，R1Is composed of
Figure GDA0003058132050000111
Wherein n is 8-12; and m is 5-10. Compared with the prior art, the gasoline detergent provided by the invention takes Mannich base with a specific structure as a main agent, has low decomposition temperature, is not decomposed in an air intake system, can better clean deposits of an air intake valve and an oil nozzle, can be decomposed into micromolecular components after fuel reaches a combustion chamber, is combusted along with the fuel, and does not additionally increase deposits in the combustion chamber; the gasoline can realize better interaction with other components with specific contents, is not easy to cause oil emulsification, can meet the requirements of gasolines with different types and different components, and has strong universality; the product can be used in the vehicle fuel oil to inhibit the generation of fuel oil system deposits, disperse and remove the generated oxidized deposits, ensure the normal exertion of the dynamic property of the vehicle, improve the combustion performance of the fuel oil, further reduce the emission of pollutants and save the oil consumption.
In addition, the preparation method provided by the invention is simple in process, mild in condition, suitable for large-scale industrial production and wide in application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The Mannich bases used in the following examples of the invention have the structural formula shown in formula (I):
Figure GDA0003058132050000112
in the formula (I), R1Is composed of
Figure GDA0003058132050000113
Wherein n is 8; m is 6;
the preparation method of the Mannich base comprises the following steps:
(1) 0.1mol of phenol, 40mL of toluene and 0.015mol of boron trifluoride (catalyst) are added into a four-neck flask, and a stirrer, a condenser tube, a separating funnel and a thermometer are arranged on the four-neck flask; dissolving 0.05mol of high-activity polyisobutylene in toluene, placing the solution in a separating funnel, introducing nitrogen to keep the normal pressure, controlling the reaction temperature to be 80 ℃, and then dropwise adding the high-activity polyisobutylene in the separating funnel for 3 hours; after the reaction is finished, standing, taking out an organic layer after the catalyst is completely deposited to the bottom of the four-neck flask, washing for 3-5 times by using hot water to remove unreacted phenol and the catalyst, standing and cooling, carrying out suction filtration to remove insoluble substances, and distilling the filtrate under reduced pressure to remove the solvent and unreacted micromolecular substances to obtain the polyisobutene phenol; the structural formula is shown in formula (II):
Figure GDA0003058132050000121
in the formula (II), R1Is composed of
Figure GDA0003058132050000122
Wherein n is 8;
(2) mixing the polyisobutylene phenol obtained in the step (1) and ethylene oxide according to a molar ratio of 1: 6, putting the mixture into a high-pressure reactor, adding Raney nickel accounting for 0.5 percent of the total mass as a catalyst, reacting for 3 hours at the temperature of 220 ℃ and the pressure of 0.5MPa, cooling to 60 ℃, carrying out suction filtration to remove insoluble substances, and distilling the filtrate under reduced pressure to obtain the p-polyisobutenyl polyoxyethylene ether; the structural formula is shown in formula (III):
Figure GDA0003058132050000123
in the formula (III), R1Is composed of
Figure GDA0003058132050000124
Wherein n is 8; m is 6;
(3) adding 0.1mol of the p-polyisobutenyl polyoxyethylene ether obtained in the step (2) and 60mL of toluene into a four-mouth bottle, adding 0.2g of p-toluenesulfonic acid serving as a catalyst, starting heating and stirring, adding diethylenetriamine into the four-mouth bottle when the temperature rises to 60 ℃, introducing nitrogen to keep normal pressure, rapidly adding paraformaldehyde in batches, continuously heating to the reflux temperature, keeping the temperature for reaction, ending the reaction until no water is generated in a water separator, cooling the reaction mixture in the four-mouth bottle to 60 ℃, performing suction filtration to remove insoluble substances, and distilling the filtrate under reduced pressure to obtain the Mannich base with the structure shown in the formula (I).
The demulsifying components comprise isooctyl alcohol, isoamyl alcohol, N-diethylhydroxylamine and lauryl polyoxyethylene ether according to the mass ratio of 10: 5: 35: 45 and compounding the mixture.
Example 1
Adding 15 parts by weight of the Mannich base, 5 parts by weight of demulsifying component, 18 parts by weight of dimethyl carbonate, 6 parts by weight of benzotriazole, 1 part by weight of tetradecenyl succinic acid and 55 parts by weight of dearomatization solvent oil into a reaction kettle, and stirring and mixing uniformly at 50 ℃ to obtain the gasoline detergent.
Example 2
Adding 20 parts by weight of the Mannich base, 7 parts by weight of demulsifying component, 15 parts by weight of polyisobutylene succinamide, 10 parts by weight of T511 antioxidant, 1.5 parts by weight of imidazoline polyoxypropylene ether and 46.5 parts by weight of white oil into a reaction kettle, and stirring and mixing uniformly at 50 ℃ to obtain the gasoline detergent.
Example 3
Adding 35 parts by weight of the Mannich base, 4 parts by weight of demulsifying component, 12 parts by weight of polyisobutylene succinimide, 12 parts by weight of 2, 6-di-tert-butylphenol, 0.6 part by weight of N-benzylpyridine and 36.4 parts by weight of dearomatization solvent oil into a reaction kettle, and stirring and mixing uniformly at 50 ℃ to obtain the gasoline detergent.
Comparative example
The market-available 1 is domestic 1 gasoline detergent;
the market 2 is domestic 2 gasoline detergent;
the commercial 3 is the international 1 gasoline detergent;
commercial 4 is the international 2 gasoline detergent.
The performances of the gasoline detergents provided in examples 1 to 3 and the comparative example were tested according to GB/T18297-2001, test methods for automobile engine performances, and the results are shown in FIGS. 1 to 7.
As can be seen from FIGS. 1 to 7, the gasoline detergent provided by the invention has excellent performances and is obviously superior to the existing products in the market; the Mannich base serving as the main agent of the gasoline detergent is low in decomposition temperature and does not decompose in an air inlet system, deposits of an air inlet valve and an oil nozzle can be better cleaned, the deposits can be decomposed into small molecular components after fuel reaches a combustion chamber and can be combusted along with the fuel without additionally increasing the deposits of the combustion chamber, the deposit increment of the combustion chamber is lower than 4%, the deposits of a commercial product cannot be decomposed in the combustion chamber, the deposits of the combustion chamber are increased, and the deposit increment of the combustion chamber is 20% -40%.
Moreover, the gasoline detergent provided by the invention is not easy to cause oil emulsification; the demulsifying component of the gasoline detergent provided by the invention can effectively solve the problem that the emulsibility of an oil product added with the detergent is poor.
In addition, the gasoline detergent provided by the invention can meet the requirements of gasolines with different types and components (different olefin and aromatic hydrocarbon contents), has better detergent performance aiming at gasoline with high aromatic hydrocarbon, high olefin and high alkane (as shown in figure 8, different raw material types and processing technologies determine the composition of the gasoline with different differences, on the basis of the research on the matching property of the finished product oil and the detergent, through a large amount of data research and analysis, the invention discovers that the finished product oil can be divided into three types of components according to the detergent sensitivity of the oil, and the detergent product meeting the detergent performance of the three types of components has higher universality, and the gasoline detergent provided by the invention has good detergent effect and good universality through the tests on the oils with different types of components, meets the requirements of gasolines with different regions and different labels, and the market product mainly aims at several types or several types of oils, when the composition and the property of the oil product are changed, the ideal detergency effect is often not achieved), the universality is good, and different grades of detergents do not need to be set for different types of gasoline independently.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A gasoline detergent comprises the following components:
15-35 parts by weight of Mannich base;
3-8 parts of a demulsifying component;
10-20 parts of octane number promoting component;
5-12 parts of antioxidant component;
0.5 to 2 parts by weight of a corrosion inhibiting component;
30-60 parts of solvent oil;
the Mannich base has the structure shown in formula (I):
Figure FDA0003058132040000011
in the formula (I), R1Is composed of
Figure FDA0003058132040000012
Wherein n is 8-12; m is 5-10;
the preparation method of the Mannich base comprises the following steps:
a) mixing phenol and high-activity polyisobutylene in a solvent, and carrying out a first reaction in the presence of a first catalyst to obtain polyisobutylene phenol with a structure shown in a formula (II);
Figure FDA0003058132040000013
in the formula (II), R1Is composed of
Figure FDA0003058132040000014
Wherein n is 8-12;
b) mixing the polyisobutylene phenol obtained in the step a) and ethylene oxide according to a molar ratio of 1: (5-10), and carrying out a second reaction in the presence of a second catalyst to obtain p-polyisobutenyl polyoxyethylene ether with a structure shown in a formula (III);
Figure FDA0003058132040000021
in the formula (III), R1Is composed of
Figure FDA0003058132040000022
Wherein n is 8-12; m is 5-10;
c) mixing the p-polyisobutenyl polyoxyethylene ether obtained in the step b), diethylenetriamine and paraformaldehyde in a solvent, and carrying out a third reaction in the presence of a third catalyst to obtain the Mannich base with the structure shown in the formula (I).
2. The gasoline detergent as claimed in claim 1, wherein the temperature of the second reaction in step b) is 200-280 ℃, the pressure is 0.5-1 MPa, and the time is 2-4 h.
3. The gasoline detergent as claimed in claim 1, wherein the demulsifying component is formed by mixing, by mass, 10: (3-8): (30-40): (40-50) isooctyl alcohol, isoamyl alcohol, N-diethylhydroxylamine and lauryl alcohol polyoxyethylene ether.
4. The gasoline detergent of claim 1, wherein the octane boosting component is selected from one or more of dimethyl carbonate, polyisobutylene succinimide, and polyisobutylene succinimide.
5. The gasoline detergent of claim 1, wherein the antioxidant component is selected from one or more of 2, 6-di-tert-butylphenol, T511 antioxidant and T531 antioxidant.
6. The gasoline detergent of claim 1, wherein the corrosion inhibiting component is selected from one or more of imidazoline polyoxypropylene ether, N-benzylpyridine, and tetradecenyl succinic acid.
7. The gasoline detergent of claim 1, wherein the mineral spirit is selected from dearomatized mineral spirits and/or white oils.
8. A method for preparing the gasoline detergent as claimed in any one of claims 1 to 7, which comprises the following steps:
the Mannich base, the demulsifying component, the octane number improving component, the antioxidant component, the corrosion inhibiting component and the solvent oil are uniformly mixed to obtain the gasoline detergent.
9. The method according to claim 8, wherein the mixing is carried out by stirring; the stirring temperature is 30-60 ℃.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962584A (en) * 2010-08-30 2011-02-02 深圳市超美化工科技有限公司 Gasoline detergent with cleaning function and preparation method thereof
CN105695007A (en) * 2016-02-26 2016-06-22 北京雅士科莱恩石油化工有限公司 Gasoline cleansing agent containing friction modifier and capable of saving fuel oil and preparation method of gasoline cleansing agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962584A (en) * 2010-08-30 2011-02-02 深圳市超美化工科技有限公司 Gasoline detergent with cleaning function and preparation method thereof
CN105695007A (en) * 2016-02-26 2016-06-22 北京雅士科莱恩石油化工有限公司 Gasoline cleansing agent containing friction modifier and capable of saving fuel oil and preparation method of gasoline cleansing agent

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