Engine fuel detergent and preparation method thereof

Abstract

The present invention relates to the field of automobile deposit cleaning technology, and specifically to an engine fuel detergent and a preparation method thereof. The engine fuel detergent of the present invention comprises the following components by weight: 30%-50% of a composite detergent, 1.5%-5% of an antioxidant, 2%-3.5% of a rust inhibitor, 1%-2% of a demulsifier, and the remainder is solvent oil; the composite detergent is a mixture of polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 40-60:1-5:35-59, which can not only greatly reduce the amount of carbon deposits on the intake valve, but also reduce the amount of carbon deposits in the engine combustion chamber, save fuel consumption, reduce the emission of toxic and harmful gases, play a role in saving resources and protecting the environment, and can be widely used in the field of automobile engine cleaning technology.

Description

Technical Field

[0001] The invention relates to the technical field of automobile carbon deposit cleaning, and in particular to an engine fuel detergent and a preparation method thereof. Background Art

[0002] At present, cars, as the main means of transportation, have penetrated into our lives. With the continuous advancement and development of technology, performance is also constantly improving. Usually, after a new car has been driving for a period of time, a series of problems such as increased fuel consumption will occur. The main reason is the poor quality of crude oil and poor refining technology, which leads to a high content of unsaturated hydrocarbons and sulfur and nitrogen compounds in automotive gasoline. As a result, during the combustion process of gasoline, carbon deposits are easily formed in the injector, intake valve, combustion chamber and other parts, which in turn causes a series of problems such as poor engine fuel supply, incomplete combustion, and increased fuel consumption.

[0003] There are three main methods for cleaning carbon deposits on fuel injectors. One is to dismantle the engine, remove the injectors, and then perform ultrasonic vibration or use a cleaning machine to clean the injectors. Although this method cleans relatively cleanly, it requires the removal of the engine, which requires a lot of manpower and material resources, resulting in high costs. It will also damage the engine and affect the tightness of the reinstalled engine parts, which will affect the performance and service life of the engine. The other is a non-disassembly cleaning agent, which cleans the engine through an external device. This method does not require the removal of the engine and will not damage the engine, but the cleaning agent technology used is not mature enough, which will cause corrosion to the equipment and insufficient subsequent fuel combustion. The third is an additive cleaning agent, which adds the cleaning agent to the fuel and cleans it during the operation of the engine. This method needs to be run for a period of time before it will be effective.

[0004] Patent technical document CN113999736A discloses a cleaning agent for a fuel intake system and a preparation method thereof. The cleaning agent prepared by this method can both dissolve and remove organic sludge inside the engine and dissolve trace moisture inside the engine, and has a good cleaning effect. However, the cleaning agent is mainly composed of macromolecular organic matter, which is difficult to fully burn in the combustion chamber, resulting in an increase in the amount of carbon deposits in the combustion chamber. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide an engine fuel detergent and a preparation method thereof to solve the problem of more deposits on the engine intake valve and combustion chamber.

[0006] Based on the above purpose, the present invention provides an engine fuel detergent, comprising the following components by weight: 30%-50% of a composite detergent, 1.5%-5% of an antioxidant, 2%-3.5% of a rust inhibitor, 1%-2% of a demulsifier, and the remainder being solvent oil;

[0007] The composite detergent is a mixture of polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 40-60:1-5:35-59;

[0008] The preparation steps of the modified polyetheramine are as follows:

[0009] S1: 1-Hydroxyethylferrocene and a phase transfer catalyst are mixed, followed by the addition of epichlorohydrin, and the mixture is subjected to extraction, washing, drying and purification at 25-30°C for 7-9 hours to obtain ferrocene epoxide;

[0010] S2: Under a nitrogen atmosphere, n-butanol and sodium hydroxide are mixed, reacted at 100-110° C. for 0.5 h, and then ethylene oxide, propylene oxide, ferrocene epoxide, and styrene oxide are added to the reaction system, reacted at 130° C. for 2-3 h, cooled, and filtered to obtain a modified polyether;

[0011] S3: Under a nitrogen atmosphere, the modified polyether and diethylenetriamine were mixed and stirred at room temperature for 30 minutes to obtain a modified polyetheramine.

[0012] Preferably, the antioxidant is 2,6-di-tert-butyl-4-methylphenol.

[0013] Preferably, the rust inhibitor is one of sorbitol fatty acid ester, triethanolamine oleate, pentaerythritol lanolin, heptadecenyl imidazoline succinate, and dodecenyl succinic acid.

[0014] Preferably, the demulsifier is one of polyoxypropylene polyoxyethylene propylene glycol ether and polyethylene oxide-propylene oxide ether.

[0015] Preferably, the solvent oil is one of poly-α-olefin synthetic oil and polyether synthetic oil.

[0016] Preferably, the relative molecular mass of the polyetheramine is 1000-2000.

[0017] Preferably, in step S1, the weight ratio of 1-hydroxyethylferrocene, phase transfer catalyst and epichlorohydrin is 200-250:55-65:130-150.

[0018] Preferably, the phase transfer catalyst in step S1 is a mixture of sodium hydroxide and tetrabutylammonium iodide in a weight ratio of 60:0.2.

[0019] Preferably, the extraction in step S1 is performed three times using dichloromethane.

[0020] Preferably, in step S2, the weight ratio of n-butanol, sodium hydroxide, ethylene oxide, propylene oxide, ferrocene epoxide, and styrene oxide is 10:0.1-0.2:100:100:1-5:1-3.

[0021] Preferably, the weight ratio of the modified polyether to diethylenetriamine in step S2 is 10:1.

[0022] Furthermore, the present invention also provides a method for preparing an engine fuel detergent, comprising the following steps:

[0023] The raw materials are mixed according to proportions and stirred sufficiently to obtain an engine fuel detergent.

[0024] Beneficial effects of the present invention:

[0025] (1) The present invention makes the distribution of ferrocene more uniform by grafting ferrocene onto the molecular chain of polyetheramine. Under the high temperature of the engine combustion chamber, the reaction between the polyetheramine and the sediment can be promoted through the catalytic effect of ferrocene, thereby improving the cleaning performance of the detergent. At the same time, the grafting of ferrocene not only improves the thermal stability of the polyetheramine, but also enhances the oil solubility of the polyetheramine, thereby enabling it to have good cleaning performance under the high temperature of the engine combustion chamber.

[0026] (2) The present invention introduces a benzene ring structure during the process of modifying the polyetheramine. On the one hand, the oil solubility of the polyetheramine is enhanced, and on the other hand, the thermal stability of the polyetheramine is improved, thereby improving the cleaning performance of the fuel detergent.

[0027] (3) The present invention introduces ferrocene and benzene rings in the process of modifying polyetheramine, and the two have a synergistic effect, which may be caused by π-π conjugation, and together improve the cleaning performance of the fuel detergent. DETAILED DESCRIPTION

[0028] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0029] The relative molecular mass of the polyetheramine used in the examples and comparative examples of the present invention is 1500; 1-hydroxyethylferrocene was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. with the item number H157110.

[0030] Example 1: An engine fuel detergent, the specific preparation steps are as follows:

[0031] (1) 200 g of 1-hydroxyethyl ferrocene and 55 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 130 g of epichlorohydrin, and the mixture was incubated at 25° C. for 7 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0032] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.1 g of sodium hydroxide were mixed and reacted at 100° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, 1 g of ferrocene epoxide, and 1 g of styrene oxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, the temperature was lowered, and the mixture was filtered to obtain a modified polyether;

[0033] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0034] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 40:1:59, and stirring to obtain a composite detergent;

[0035] (5) 30 g of the composite detergent, 1.5 g of 2,6-di-tert-butyl-4-methylphenol, 2 g of sorbitol fatty acid ester, 1 g of polyethylene oxide-propylene oxide ether and 65.6 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0036] Example 2: An engine fuel detergent, the specific preparation steps are as follows:

[0037] (1) 225 g of 1-hydroxyethyl ferrocene and 60 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 140 g of epichlorohydrin, and the mixture was incubated at 28° C. for 8 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0038] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.15 g of sodium hydroxide were mixed and reacted at 105° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, 3 g of ferrocene epoxide, and 2 g of styrene oxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, and the temperature was lowered and filtered to obtain a modified polyether;

[0039] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0040] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 50:3:47, and stirring to obtain a composite detergent;

[0041] (5) 40 g of the composite detergent, 3.5 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 1.5 g of polyethylene oxide-propylene oxide ether and 52 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0042] Example 3: An engine fuel detergent, the specific preparation steps are as follows:

[0043] (1) 240 g of 1-hydroxyethyl ferrocene and 63 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 150 g of epichlorohydrin, and the mixture was incubated at 30° C. for 7 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0044] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.2 g of sodium hydroxide were mixed and reacted at 100° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, 4 g of ferrocene epoxide, and 3 g of styrene oxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, and the temperature was lowered and filtered to obtain a modified polyether;

[0045] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0046] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 50:3:47, and stirring to obtain a composite detergent;

[0047] (5) 45 g of the composite detergent, 4 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 2 g of polyethylene oxide-propylene oxide ether and 46 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0048] Example 4: An engine fuel detergent, the specific preparation steps are as follows:

[0049] (1) 250 g of 1-hydroxyethyl ferrocene and 65 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 150 g of epichlorohydrin, and the mixture was incubated at 30° C. for 9 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0050] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.2 g of sodium hydroxide were mixed and reacted at 110° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, 5 g of ferrocene epoxide, and 3 g of styrene oxide were added to the reaction system, and the mixture was reacted at 130° C. for 2-3 h, cooled, and filtered to obtain a modified polyether;

[0051] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0052] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 60:5:35, and stirring evenly to obtain a composite detergent;

[0053] (5) 50 g of the composite detergent, 5 g of 2,6-di-tert-butyl-4-methylphenol, 3.5 g of sorbitol fatty acid ester, 2 g of polyethylene oxide-propylene oxide ether and 39.5 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0054] Comparative Example 1: An engine fuel detergent, the specific preparation steps are as follows:

[0055] (1) Under a nitrogen atmosphere, 10 g of n-butanol and 0.15 g of sodium hydroxide were mixed and reacted at 105° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, and 2 g of styrene oxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, and the temperature was lowered and filtered to obtain a modified polyether;

[0056] (2) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0057] (3) mixing polyetheramine, modified polyetheramine, 1-hydroxyethylferrocene and polyisobutylene succinimide in a weight ratio of 50:2.95:0.05:47, and stirring to obtain a composite detergent;

[0058] (4) 40 g of the composite detergent, 3.5 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 1.5 g of polyethylene oxide-propylene oxide ether and 52 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0059] Comparative Example 2: An engine fuel detergent, the specific preparation steps are as follows:

[0060] (1) 225 g of 1-hydroxyethyl ferrocene and 60 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 140 g of epichlorohydrin, and the mixture was incubated at 28° C. for 8 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0061] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.15 g of sodium hydroxide were mixed and reacted at 105° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, and 2 g of styrene oxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, and the temperature was lowered and filtered to obtain a modified polyether;

[0062] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0063] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 50:3:47, and stirring to obtain a composite detergent;

[0064] (5) 40 g of the composite detergent, 3.5 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 1.5 g of polyethylene oxide-propylene oxide ether and 52 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0065] Comparative Example 3: An engine fuel detergent, the specific preparation steps are as follows:

[0066] (1) 225 g of 1-hydroxyethyl ferrocene and 60 g of a phase transfer catalyst (sodium hydroxide and tetrabutylammonium iodide mixed in a weight ratio of 60:0.2) were added, followed by 140 g of epichlorohydrin, and the mixture was incubated at 28° C. for 8 h, extracted three times with dichloromethane, washed, dried, and purified to obtain ferrocene epoxide;

[0067] (2) Under a nitrogen atmosphere, 10 g of n-butanol and 0.15 g of sodium hydroxide were mixed and reacted at 105° C. for 0.5 h, and then 100 g of ethylene oxide, 100 g of propylene oxide, and 3 g of ferrocene epoxide were added to the reaction system, and the reaction was carried out at 130° C. for 2-3 h, and the temperature was lowered and filtered to obtain a modified polyether;

[0068] (3) Under a nitrogen atmosphere, 50 g of the modified polyether and 5 g of diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine;

[0069] (4) mixing polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 50:3:47, and stirring to obtain a composite detergent;

[0070] (5) 40 g of the composite detergent, 3.5 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 1.5 g of polyethylene oxide-propylene oxide ether and 52 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0071] Comparative Example 4: An engine fuel detergent, the specific preparation steps are as follows:

[0072] (1) mixing polyetheramine and polyisobutylene succinimide in a weight ratio of 53:47, and stirring to obtain a composite detergent;

[0073] (2) 40 g of the composite detergent, 3.5 g of 2,6-di-tert-butyl-4-methylphenol, 3 g of sorbitol fatty acid ester, 1.5 g of polyethylene oxide-propylene oxide ether and 52 g of polyether synthetic oil were mixed and stirred thoroughly to obtain an engine fuel detergent.

[0074] Performance Testing

[0075] Simple transient operating condition method: A certain amount of the detergent obtained in the embodiment and the comparative example was added to E10 92# ethanol gasoline, so that the content of the detergent obtained in the embodiment and the comparative example was 500 PPM. According to the simple transient operating condition method in GB 18285-2018 Emission limits and measurement methods of pollutants for gasoline vehicles (dual idle method and simple operating condition method), the effects of the detergent obtained in the embodiment and the comparative example on the carbon deposition of the engine intake valve and the combustion chamber and the fuel consumption were measured before and after adding the detergent obtained in the embodiment and the comparative example, and a real vehicle experiment was carried out for 350 hours. The test results are shown in Table 1;

[0076] Dual idle test experiment: A certain amount of the detergent obtained in the embodiment and the comparative example was added to E10 92# ethanol gasoline so that the content of the detergent obtained in the embodiment and the comparative example was 500PPM. According to GB 18285-2018 Emission limits and measurement methods for pollutants from gasoline vehicles (dual idle method and simple operating condition method), dual idle tests were carried out before and after the detergent obtained in the embodiment and the comparative example was added to investigate its effects on exhaust emissions under idle and high idle conditions. The test results are shown in Table 1.

[0077] Table 1 Performance test results

[0078]

[0079] Data analysis: The engine fuel purifier of the present invention can significantly reduce the amount of carbon deposits on the intake valve, and can reduce the amount of carbon deposits in the engine combustion chamber to a certain extent, and reduce the average fuel consumption, thereby saving fuel resources; at the same time, it can significantly reduce the emission of automobile exhaust pollutants, thereby protecting the environment.

[0080] It can be seen from Example 2 and Comparative Examples 1 and 2 that the present invention makes the distribution of ferrocene more uniform by grafting ferrocene onto the molecular chain of polyetheramine, and can promote the reaction of polyetheramine with sediments through catalysis at the high temperature of the engine combustion chamber, thereby improving the cleaning performance of the detergent; at the same time, the grafting of ferrocene not only improves the thermal stability of the polyetheramine, but also enhances the oil solubility of the polyetheramine, thereby enabling it to have good cleaning performance at the high temperature of the engine combustion chamber.

[0081] It can be seen from Example 2 and Comparative Example 3 that the present invention introduces a benzene ring structure during the process of modifying the polyetheramine, which, on the one hand, enhances the oil solubility of the polyetheramine, and on the other hand, also improves the thermal stability of the polyetheramine, thereby improving the cleaning performance of the fuel detergent.

[0082] It can be seen from Example 2 and Comparative Examples 2, 3 and 4 that the present invention introduces ferrocene and benzene ring in the process of modifying polyetheramine, and the two have a synergistic effect, which may be caused by π-π conjugation, and together improves the cleaning performance of the fuel detergent.

[0083] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention (including the claims) is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0084] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An engine fuel detergent, characterized in that: It includes the following components by weight: 30%-50% of composite detergent, 1.5%-5% of antioxidant, 2%-3.5% of rust inhibitor, 1%-2% of demulsifier, and the rest is solvent oil; The composite detergent is a mixture of polyetheramine, modified polyetheramine and polyisobutylene succinimide in a weight ratio of 40-60:1-5:35-59; The preparation steps of the modified polyetheramine are as follows: S1: 1-hydroxyethylferrocene and a phase transfer catalyst are mixed, epichlorohydrin is then added, the mixture is reacted at 25-30°C for 7-9h, and ferrocene epoxide is obtained by extraction, washing, drying and purification; S2: Under a nitrogen atmosphere, n-butanol and sodium hydroxide are mixed, reacted at 100-110° C. for 0.5 h, and then ethylene oxide, propylene oxide, ferrocene epoxide, and styrene oxide are added to the reaction system, reacted at 130° C. for 2-3 h, cooled, and filtered to obtain a modified polyether; S3: Under a nitrogen atmosphere, the modified polyether and diethylenetriamine were mixed and stirred at room temperature for 30 min to obtain a modified polyetheramine; The weight ratio of 1-hydroxyethylferrocene, phase transfer catalyst and epichlorohydrin in step S1 is 200-250:55-65:130-150; The weight ratio of n-butanol, sodium hydroxide, ethylene oxide, propylene oxide, ferrocene epoxide and styrene oxide in step S2 is 10:0.1-0.2:100:100:1-5:1-3.

2. The engine fuel detergent according to claim 1, characterized in that: The antioxidant is 2,6-di-tert-butyl-4-methylphenol.

3. The engine fuel detergent according to claim 1, characterized in that: The rust inhibitor is one of sorbitol fatty acid ester, triethanolamine oleate, pentaerythritol lanolin, heptadecenyl imidazoline succinate, and dodecenyl succinic acid.

4. The engine fuel detergent according to claim 1, characterized in that: The demulsifier is one of polyoxypropylene polyoxyethylene propylene glycol ether and polyethylene oxide-propylene oxide ether.

5. The engine fuel detergent according to claim 1, characterized in that: The solvent oil is one of poly-α-olefin synthetic oil and polyether synthetic oil.

6. The engine fuel detergent according to claim 1, characterized in that: The relative molecular mass of the polyetheramine is 1000-2000.

7. The engine fuel detergent according to claim 1, characterized in that: The weight ratio of the modified polyether to diethylenetriamine in step S2 is 10:

1.

8. A method for preparing an engine fuel detergent according to any one of claims 1 to 7, characterized in that: The steps include: The raw materials are mixed according to proportions and stirred sufficiently to obtain an engine fuel detergent.

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