A gasoline high-efficiency composite additive and a preparation method thereof

Abstract

The present application belongs to the field of gasoline additives for vehicles, and particularly relates to a high-efficiency composite gasoline additive and a preparation method thereof. The high-efficiency composite gasoline additive comprises the following components: a detergent 30-60%, a dispersant 10-20%, a demulsifier 1-5%, a corrosion and rust inhibitor 1-5%, and solvent oil in a residual amount. The detergent comprises Mannich base and polyether amine, and the mass ratio of the two substances is 8:9-7:5. The additive has a small injection amount, and has a good cleaning effect on both simulated intake valves and combustion chamber deposits. The additive can significantly reduce the emission of environmental gas pollutants.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a high-efficiency composite additive for gasoline and its preparation method. Background Technology

[0002] In recent years, with rapid economic growth, the number of cars in my country has increased significantly. Therefore, reducing vehicle exhaust emissions, controlling the total amount of pollutants emitted by motor vehicles, and effectively improving urban air quality are of great significance.

[0003] While new alternative fuels (such as ethanol gasoline, biofuels, and fuel cells) are currently a hot research topic, they cannot completely replace existing gasoline and diesel fuels in the short term. A relatively effective and economical way to reduce engine deposits and thus vehicle emissions is to add gasoline detergents to the fuel. Gasoline detergents can improve fuel economy, reduce vehicle maintenance costs, lower vehicle emissions, and protect the atmospheric environment, offering significant social and economic benefits. However, due to the inconsistent quality of detergent products on the market, most detergents are only evaluated using the L-2 type gasoline engine simulated intake valve deposit test method, without undergoing the more widely accepted engine bench test, making their actual effectiveness difficult to guarantee. Furthermore, the current recommended dosage for gasoline detergents to meet the simulated intake valve deposit quality requirements is 500-1000 ppm, which is too high. This increases deposits in the engine combustion chamber, reduces combustion efficiency, and prevents the detergent from significantly achieving its energy-saving and emission-reduction effects. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a high-efficiency composite additive for gasoline and its preparation method. This additive exhibits excellent cleaning effects on both intake valve and combustion chamber deposits, significantly reducing environmental gaseous pollutant emissions. When the additive is added at a dosage of 300-400 ppm, an intake valve deposit reduction rate exceeding 93% was achieved using an L-2 gasoline engine simulated by a deposit test method. Using the M111 bench test method, the deposit reduction rate exceeded 95%, with combustion chamber deposits increasing by no more than 10%. Vehicle emissions testing using a Volkswagen Tayron 2.0T vehicle showed a 30.5% reduction in hydrocarbons, a 32.4% reduction in carbon monoxide, and a 15.68% reduction in NOx.

[0005] The technical solution of the present invention is as follows:

[0006] A high-efficiency composite additive for gasoline, comprising the following components by weight percentage:

[0007]

[0008] The detergent comprises two substances: Mannich base and polyetheramine, with a mass ratio of Mannich base to polyetheramine of 8:9-7:5.

[0009] Preferably, the molecular weight of the Mannich base is 900-1300, the total amine value of the polyether amine is 0.95-1.05 meq / g, and the primary amine content is ≥97%.

[0010] Preferably, the composite additive, by weight percentage, comprises the following components:

[0011]

[0012]

[0013] Preferably, the dispersant is nonylphenol polyoxypropylene ether. More preferably, the hydroxyl value of nonylphenol polyoxypropylene ether is 55-60.

[0014] Preferably, the demulsifier is one or both of PX-3843 and PX-3841.

[0015] Preferably, the corrosion and rust inhibitor is N-oleoylsarcosine octadecylamine salt.

[0016] Preferably, the solvent oil is a high-boiling-point aromatic solvent SA1500.

[0017] A method for preparing a high-efficiency composite additive for gasoline includes the following steps:

[0018] a) Thoroughly mix the detergent, dispersant, demulsifier, and solvent oil;

[0019] b) Add corrosion and rust inhibitors to the above mixture (30-40℃ insulation is required in winter), then mix evenly to obtain a high-efficiency gasoline composite additive.

[0020] Preferably, the temperature required for mixing and homogenization is 25℃~45℃; the time required for homogenization is 1~3h.

[0021] This invention improves the thermal stability of gasoline detergents by optimizing the type and ratio of Mannich base and polyetheramine, fully leveraging their cleaning performance at high temperatures while minimizing their impact on combustion chamber deposits. The combination effectively controls deposit formation on high-temperature components of gasoline engines, reducing the rate of deposit formation in the fuel system, intake system, and combustion chamber. Nonylphenol polyoxypropylene ether exhibits good low-temperature stability and solubility, ensuring the product remains clear and free from precipitation at -15°C. The corrosion and rust inhibitor is N-oleoylsarcosine octadecylamine salt, possessing good rust prevention and demulsification properties, and a low acid value. PX-3843 and PX-3841 are silicone-free additives with demulsifying and continuous defoaming effects, along with good thermal stability and dispersion characteristics. The selection of SA1500, with its high flash point, ensures that the flash point of the high-efficiency composite additive meets GB standards. The requirement of a flash point of ≥60℃ in 19592-2019, along with an octane number of not less than 110 for SA1500, can improve its anti-knock properties when added to gasoline.

[0022] The high-efficiency composite additive of this invention exhibits excellent cleaning properties even at a dosage of 300-400 ppm, thanks to the synergistic formulation of its raw materials. It provides anti-rust protection for engine metal parts and remains clear even at -15℃, ensuring uniform dispensing during winter applications. Experimental results show that, at a dosage of 300-400 ppm, the gasoline high-efficiency composite additive of this invention reduces deposits by over 93% using the L-2 gasoline engine simulated intake valve deposit test method; using the M111 bench test method, the deposit reduction rate exceeds 95%, with combustion chamber deposits increasing by no more than 10%; and in a Volkswagen Tayron 2.0T vehicle emissions test, hydrocarbons decreased by 30.5%, carbon monoxide by 32.4%, and NOx by 15.68%. This gasoline high-efficiency composite additive effectively cleans both simulated intake valve and combustion chamber deposits, significantly reducing environmental gaseous pollutant emissions.

[0023] This invention provides a gasoline composite additive that requires a small dosage and effectively cleans deposits from both the simulated intake valve and combustion chamber, significantly reducing environmental gaseous pollutant emissions. It has been evaluated using both the L-2 gasoline engine simulated intake valve deposit test method and the M111 bench test method, and has also been tested using a Volkswagen Tayron 2.0T vehicle for overall vehicle emissions testing, all yielding excellent results. This demonstrates that the cleaning effect and pollutant emission reduction effect of the gasoline composite additive are effectively guaranteed. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] This invention provides a high-efficiency composite additive for gasoline, comprising the following components by mass percentage:

[0026]

[0027]

[0028] In this invention, the detergent is composed of two substances: Mannich base and polyetheramine. The molecular weight of Mannich base is 900-1300, the total amine value of polyetheramine is 0.95-1.05 meq / g, the primary amine content is not less than 97%, and the mass ratio of Mannich base to polyetheramine is 8:9-7:5. The combination of the two can effectively control the formation of deposits on high-temperature components of gasoline engines and reduce the deposit formation rate in the engine fuel system, intake system, combustion chamber, and other parts.

[0029] The detergent content in the raw materials is 30% to 60%, specifically 30%, 35%, 37%, 40%, 45%, 50%, 56%, or 60%.

[0030] The dispersant used in this invention is nonylphenol polyoxypropylene ether, with a hydroxyl value of 55-60. Nonylphenol polyoxypropylene ether exhibits good low-temperature stability and solubility, ensuring the product remains clear and free from precipitation at -15°C. The content of the dispersant in the raw material is 10-20%, specifically 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.

[0031] In this invention, the demulsifier is one or more of PX-3843 and PX-3841. The aforementioned demulsifier is a silicone-free additive that has the functions of demulsification and continuous defoaming, while also possessing good thermal stability and dispersing properties. The content of the demulsifier in the raw material is 1-5%, specifically 1%, 1.5%, 2%, 3%, 4%, or 5%.

[0032] In this invention, the corrosion and rust inhibitor is N-oleoylsarcosine octadecylamine salt, which has better rust prevention and demulsification properties than conventional dodecenylsuccinic acid, and has a lower acid value. The content of the corrosion and rust inhibitor in the raw material is 1-5%, specifically 1%, 1.5%, 2%, 3%, 4%, or 5%.

[0033] The solvent oil used in this invention is a high-boiling-point aromatic solvent SA1500, which has a high flash point, enabling the flash point of the high-efficiency composite additive to meet the requirement of flash point ≥60℃ in GB 19592-2019. At the same time, the octane number of SA1500 is not less than 110, which can improve the anti-knock properties when added to gasoline.

[0034] The preparation method of the above-mentioned high-efficiency composite additive for gasoline includes the following steps:

[0035] a) Thoroughly mix the detergent, dispersant, demulsifier, and solvent oil;

[0036] b) Add corrosion and rust inhibitors to the above mixture (the corrosion and rust inhibitors need to be kept at 30-40℃ in winter for easy removal), then mix evenly to obtain a high-efficiency gasoline composite additive.

[0037] The temperature required for mixing and homogenization is 25℃~45℃; the time required for homogenization is 1~3h.

[0038] In the preparation method provided by this invention, the detergent, dispersant, demulsifier, and solvent oil are first mixed in proportion. Then, an anti-corrosion and anti-rust agent is added to the mixture, and then it is mixed evenly. The mixing temperature is preferably 25-45°C, specifically 25°C, 30°C, 35°C, 40°C, or 45°C; the mixing time is preferably 1-3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours.

[0039] This invention optimizes the raw material formulation of a high-efficiency gasoline composite additive, improving its compatibility and resulting in superior detergency and anti-corrosion properties. This effectively protects the engine and extends its service life. Experimental results show that when the high-efficiency gasoline composite additive provided by this invention is added at a dosage of 300-400 ppm, the deposit reduction rate exceeds 93% using the L-2 gasoline engine simulated intake valve deposit test method; using the M111 bench test method, the deposit reduction rate exceeds 95%, and the increase in combustion chamber deposits is no more than 10%. Vehicle emissions testing using a Volkswagen Tayron 2.0T vehicle showed a 34.34% reduction in hydrocarbons, a 29.94% reduction in carbon monoxide, and a 19.15% reduction in NOx. The high-efficiency gasoline composite additive possesses excellent detergency and anti-corrosion properties, significantly reducing environmental gaseous pollutant emissions.

[0040] For clarity, the following examples will be used to provide a detailed description.

[0041] Specific preparation method of Mannich base:

[0042] 15 kg of toluene, 4.5 kg of o-cresol, and 1.4 kg of boron trifluoride diethyl ether complex were added to the reactor. The temperature was raised to 48°C. A polyisobutylene solution (a mixture of 10 kg of toluene and 22 kg of polyisobutylene (Mn = 1000)) was slowly added to the reactor over 2 hours, maintaining the temperature at 50°C for 6 hours. A sample of the reaction solution was taken for hydroxyl value testing. If the hydroxyl value was within the acceptable range (50-55), the solution was washed twice with water to remove unreacted o-cresol. 1.75 kg of ethylenediamine was added, and the temperature was raised to 58°C. 2.6 kg of formaldehyde was slowly added over 2 hours, and the temperature was raised to 155°C and maintained for 4 hours. The solvent and water were then removed by vacuum distillation, and the solution was filtered to obtain 24.22 kg of Mannich base detergent. All Mannich bases used below were prepared using this method. The total amine value of the polyether amines described below is 0.95-1.05 meq / g, and the primary amine content is ≥97%.

[0043] Example 1

[0044] A high-efficiency compound additive for gasoline:

[0045] 1) Ingredient design:

[0046] 100% high-efficiency composite additive for gasoline, 56% detergent (32% Mannich base, 24% polyetheramine), 11% nonylphenol polyoxypropylene ether (hydroxyl value 58), 2% PX-3843 demulsifier, 1% N-oleoylsarcosine octadecylamine salt, and 30% SA1500 solvent oil.

[0047] 2) Preparation of high-efficiency composite additives for gasoline:

[0048] First, thoroughly mix the Mannich base, polyetheramine, nonylphenol polyoxypropylene ether, demulsifier and SA1500 solvent oil (at 25°C for 3 hours), then add N-oleoylsarcosine octadecylamine salt and stir until homogeneous. Store at room temperature.

[0049] Example 2

[0050] A high-efficiency compound additive for gasoline:

[0051] 1) Ingredient design:

[0052] 100% high-efficiency composite additive for gasoline, 50% detergent (24% Mannich base, 26% polyetheramine), 15% nonylphenol polyoxypropylene ether, 1.5% PX-3843 demulsifier, 1.5% N-oleoylsarcosine octadecylamine salt, and 32% SA1500 solvent oil.

[0053] 2) Preparation of high-efficiency composite additives for gasoline:

[0054] First, thoroughly mix the Mannich base, polyetheramine, nonylphenol polyoxypropylene ether, demulsifier and SA1500 solvent oil (temperature 40℃, time 1h), then add N-oleoylsarcosine octadecylamine salt and stir well, then store at room temperature.

[0055] Example 3

[0056] A high-efficiency compound additive for gasoline:

[0057] 1) Ingredient design:

[0058] The gasoline high-efficiency composite additive is 100%, detergent is 37% (Mannich base 22%, polyetheramine 15%), nonylphenol polyoxypropylene ether is 18%, PX-3843 demulsifier is 1%, N-oleoylsarcosine octadecylamine salt is 2%, and SA1500 solvent oil is 42%.

[0059] 2) Preparation of high-efficiency composite additives for gasoline:

[0060] First, thoroughly mix the Mannich base, polyetheramine, nonylphenol polyoxypropylene ether, demulsifier and solvent oil SA1500 (temperature 30℃, time 2h), then add N-oleoylsarcosine octadecylamine salt and stir well, then store at room temperature.

[0061] Comparative Example 1

[0062] A high-efficiency compound additive for gasoline:

[0063] The gasoline high-efficiency composite additive is 100%, detergent is 14.8% (Mannich base 4.8%, polyetheramine 10%), nonylphenol polyoxypropylene ether is 18%, PX-3843 demulsifier is 1%, N-oleoylsarcosine octadecylamine salt is 2%, and SA1500 solvent oil is 64.2%.

[0064] 2) Preparation of high-efficiency composite additives for gasoline:

[0065] First, thoroughly mix the Mannich base, polyetheramine, nonylphenol polyoxypropylene ether, demulsifier and solvent oil SA1500 (temperature 30℃, time 2h), then add N-oleoylsarcosine octadecylamine salt and stir well, then store at room temperature.

[0066] Comparative Example 2

[0067] A high-efficiency compound additive for gasoline:

[0068] 1) Ingredient design:

[0069] 100% gasoline additive, 56% detergent (32% Mannich base, 24% polyetheramine), 11% polypropylene glycol (molecular weight 1000), 2% PX-3843 demulsifier, 1% N-oleoylsarcosine octadecylamine salt, and 30% SA1500 solvent oil.

[0070] 2) Preparation of gasoline additives:

[0071] First, thoroughly mix the Mannich base, polyetheramine, polypropylene glycol, demulsifier, and SA1500 solvent oil (at 30°C for 2 hours), then add N-oleoylsarcosine octadecylamine salt and stir until homogeneous. Store at room temperature.

[0072] Comparative Example 3

[0073] A high-efficiency compound additive for gasoline:

[0074] 1) Ingredient design:

[0075] 100% gasoline additive, 56% detergent (32% Mannich base, 24% polyetheramine), 11% nonylphenol polyoxypropylene ether, 2% SP-169 demulsifier, 1% N-oleoylsarcosine octadecylamine salt, and 30% SA1500 solvent oil.

[0076] 2) Preparation of gasoline additives:

[0077] First, thoroughly mix the Mannich base, polyetheramine, nonylphenol polyoxypropylene ether, demulsifier and SA1500 solvent oil (temperature 30℃, time 2h), then add dodecenyl succinate half ester and stir until uniform, and store at room temperature.

[0078] Comparative Example 4 (using the fuel-saving gasoline detergent containing friction modifier from the best embodiment 5 of patent 2016101093271 as Comparative Example 4)

[0079] A high-efficiency compound additive for gasoline:

[0080] 1) Ingredient design:

[0081] The composition includes 100% gasoline additive, 40% Mannich base, 7% boronized polyisobutylene succinimide, 8% ethyl tert-butyl ether, 4.5% molybdenum N,N-di(dodecyl)dithiocarbamate, 0.4% antioxidant (a mixture of 50wt% 4,4'-dioctyl diphenylamine and 50wt% 4,4'-dimethyl diphenylamine), 2.2% dodecenyl succinic acid, 0.1% dimethyl silicone oil, 15% dimethyl carbonate, and the balance being di(2-ethylhexyl) azelaate.

[0082] 2) Preparation of gasoline additives:

[0083] (1) Di(2-ethylhexyl) azelate, dimethyl carbonate, Mannich base, and boronized polyisobutylene succinimide were added sequentially to the reaction mixing vessel and heated to 55°C. The mixture was stirred at 400 rpm for 0.5 h until homogeneous.

[0084] (2) Add molybdenum N,N-di(dodecyl)dithiocarbamate, antioxidant, dodecenyl succinic acid, and dimethyl silicone oil. Stir at 55°C for 0.5 h at 400 rpm until the mixture is homogeneous.

[0085] (3) Cool down to 40°C, add ethyl tert-butyl ether, stir at 400 rpm for 1 hour, and filter through a 5 μm filter to obtain the additive.

[0086] Performance testing

[0087] According to GB 19592-2019 "Automotive Gasoline Detergents", the demulsibility index of Examples 1-3 and Comparative Examples 1-4 was tested, and the detergent performance of the examples was evaluated using an L-2 type gasoline engine intake valve deposit simulation tester. Low-temperature stability was also evaluated at -15℃. The results are shown in Table 1.

[0088] Table 1 Performance Tests of High-Efficiency Composite Additives for Gasoline

[0089]

[0090]

[0091] As shown in Table 1, the gasoline high-efficiency composite additive of the present invention, when added to gasoline, resulted in a deposit reduction rate greater than 94%, and simulated intake valve deposits were all ≤0.6mg, exhibiting excellent low-temperature stability and demulsification properties. Compared to the examples, Comparative Example 1, which only replaced the amount of detergent and the ratio of Mannich base to polyetheramine, showed a significantly reduced deposit reduction rate and failed to meet demulsification standards. Comparative Example 2, which only replaced the dispersant, failed to meet the low-temperature stability standards, and simultaneously showed an increase in simulated intake valve deposits and a significantly reduced deposit reduction rate. Comparative Example 3, which only replaced the demulsifier, failed to meet demulsification standards, and simultaneously showed an increase in simulated intake valve deposits and a significantly reduced deposit reduction rate. Comparative Example 4, a gasoline additive in the prior art, showed a significant increase in simulated intake valve deposits and a reduced deposit reduction rate, indicating a significantly worse effect compared to the examples.

[0092] The cleaning performance of the embodiments was tested and evaluated using the M111 bench test method, and the test results are shown in Table 2.

[0093] Table 2 Bench Tests of High-Efficiency Composite Additives for Gasoline

[0094]

[0095] As can be seen from the table above, the gasoline high-efficiency composite additive of the present invention meets the national standard requirements when evaluated by the M111 bench test method. The intake valve deposits and combustion chamber deposits are very small, far below the national standard requirements. The intake valve deposits are ≤9mg / valve, which can be as low as 3mg, and the combustion chamber deposits are ≤12%, which can be as low as 5.6%. Moreover, the deposit reduction rate exceeds 95%.

[0096] Using a Volkswagen Tayron vehicle, the emission test evaluation of gasoline high-efficiency composite additive in Example 3 was carried out in accordance with GB18352.6-2016 "Limits and Measurement Methods for Pollutant Emissions from Light-Duty Vehicles (China VI)". The additive dosage was 400 ppm, and the results are shown in Table 3.

[0097] Table 3 Gaseous pollutant emissions

[0098]

[0099] As can be seen from the table above, when 400 ppm of the high-efficiency composite additive from Example 3 was added to 92-octane standard gasoline, the gas emissions were tested after driving 2000 km. Compared with the standard gasoline, hydrocarbon emissions decreased by 34.34%, carbon monoxide emissions decreased by 29.94%, NOx emissions decreased by 19.15%, and fuel consumption decreased by 2.71%, which is a significant improvement over existing technologies.

[0100] This invention provides a gasoline composite additive that requires a small dosage and effectively cleans deposits from both the simulated intake valve and combustion chamber, significantly reducing environmental gaseous pollutant emissions. It has been evaluated using both the L-2 gasoline engine simulated intake valve deposit test method and the M111 bench test method, and has also been tested using a Volkswagen Tayron 2.0T vehicle for overall vehicle emissions testing, all yielding excellent results. This demonstrates that the cleaning effect and pollutant emission reduction effect of the gasoline composite additive are effectively guaranteed.

[0101] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-efficiency composite additive for gasoline, characterized in that, It consists of the following components by mass percentage: Cleaning agent 30-60%; Dispersant 10-20%; Demulsifier 1-5%; Corrosion and rust inhibitor 1~5%; Solvent oil balance; The detergent comprises two substances: Mannich base and polyetheramine, with a mass ratio of Mannich base to polyetheramine of 8:9-7:

5. The dispersant is nonylphenol polyoxypropylene ether; The hydroxyl value of the nonylphenol polyoxypropylene ether is 55-60; The demulsifier is one of PX-3843 and PX-3841 or two of them in any proportion. The corrosion and rust inhibitor is N-oleoylsarcosine octadecylamine salt.

2. The gasoline high-efficiency composite additive according to claim 1, characterized in that, The Mannich base has a molecular weight of 900-1300, a total amine value of 0.95-1.05 meq / g, and a primary amine content of ≥97%.

3. The gasoline high-efficiency composite additive according to claim 1, characterized in that, It includes the following components by mass percentage: Cleaning agent 37-60%; Dispersant 11~18%; Demulsifier 1-3%; Corrosion and rust inhibitor 1~3%; Solvent oil balance.

4. The gasoline high-efficiency composite additive according to claim 1, characterized in that, The solvent oil is a high-boiling-point aromatic solvent SA1500.

5. A method for preparing the high-efficiency composite additive for gasoline according to any one of claims 1-4, comprising the following steps: a) A mixture of detergent, dispersant, demulsifier and solvent oil; b) Add corrosion and rust inhibitors to the above mixture, then mix evenly to obtain a high-efficiency gasoline composite additive.

6. The method for preparing the high-efficiency composite additive for gasoline according to claim 5, characterized in that, The required temperature for mixing and homogenization is 25℃~45℃; the required time for mixing and homogenization is 1~3h.

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