Method for preparing metal cleaning agent by ultrasonic method

Abstract

The application discloses a method for preparing a metal detergent by using an ultrasonic method, and particularly relates to the following steps: mixing oil-soluble organic acid, lubricating oil base oil, metal compound, accelerant, additive, and solvent to perform neutralization reaction and obtain a mixed solution; adding non-ionic surfactant into the mixed solution, starting an ultrasonic device, and passing in carbon dioxide until a certain free alkali value is reached, then stopping the passing in of carbon dioxide and closing the ultrasonic device, removing the solvent, additive, and water, and obtaining a crude product; adding solvent into the crude product to perform dilution, centrifuging, obtaining a filtrate, and removing the solvent to obtain the metal detergent. By means of combination of an anionic surfactant and a non-ionic surfactant, the application solves the stability problem of the metal detergent to water, methanol and the like; by means of ultrasonic technology, the application solves the dispersion problems such as mass transfer and heat transfer among the three phases of gas, solid and liquid, i.e. the anionic surfactant, the non-ionic surfactant, metal oxide, and carbon dioxide, in the preparation process of the metal detergent.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of lubricating oil detergent, and particularly relates to a method for preparing metal detergent by using ultrasonic method. BACKGROUND

[0002] Clean energy engine is powered by natural gas, methanol, hydrogen, ammonia and other fuels, which is cleaner and less polluting than gasoline and diesel engines. The polar harmful substances such as water, alcohol and acid produced by the combustion of clean fuel engine seriously damage the lubricating system, resulting in a decrease in the acid neutralization capacity of lubricating oil, a sharp drop in the base value, an acceleration of the decomposition of anti-oxidation and anti-wear agents, and the stratification of additives in the lubricating oil into flocculation and sludge precipitation. The existing solutions mainly focus on the optimization of the formula of lubricating oil. For example, a kind of methanol engine special nano energy-saving lubricating oil and its preparation method are disclosed in Chinese patent (publication number CN113322119B), in which multi-functional nano additives-dihydrocarbyl dithiophosphoric acid modified zinc oxide nanoparticles and high-temperature antioxidants are introduced to solve the problem of easy oxidation and acidification of methanol engine lubricating oil.

[0003] Since the main lubricating oil additives with the properties of acid neutralization, base value maintenance and certain anti-wear are metal detergents, it is crucial to improve the water, alcohol and acid resistance of metal detergents. Common metal detergents are generally anionic soap salt surfactants formed by organic acids and their combinations, such as different combinations of different anionic surfactants such as calcium alkyl benzene sulfonate, calcium alkyl salicylate, calcium sulfonated alkyl phenol, calcium naphthenate, calcium stearate, etc. However, the combination of anionic surfactants cannot solve the problems of acid neutralization capacity decrease, base value drop and additive stratification into flocculation caused by water, alcohol and acid. SUMMARY

[0004] The purpose of the present application is to provide a method for preparing metal detergent by using ultrasonic method, which improves the yield and stability of metal detergent.

[0005] The technical solution adopted by the present application is a method for preparing metal detergent by using ultrasonic method, which is implemented according to the following steps:

[0006] Step 1, mix and stir oil-soluble organic acid, lubricating oil base oil, metal compound, promoter, additive, and solvent to carry out neutralization reaction, and obtain anionic surfactant mixed solution;

[0007] Step 2, under the condition of 30-60℃, add non-ionic surfactant to the anionic surfactant mixed solution of step 1, start the ultrasonic device, obtain non-ionic surfactant mixed solution, then pass in carbon dioxide until a certain free base value, stop passing in carbon dioxide and turn off the ultrasonic device, remove the solvent, additive and water by heating, and obtain the crude product;

[0008] Step 3, the crude product is diluted by adding a solvent, solid residues are removed by centrifugation, a filtrate is obtained, and the solvent is removed by heating to obtain the metal detergent.

[0009] The present application is also characterized in that,

[0010] In step 1, the neutralization reaction temperature is 40-100℃, and the reaction time is 0.5h.

[0011] In step 1, the oil-soluble organic acid is any one or more of alkylbenzenesulfonic acid, alkylsalicylic acid, sulfided alkylphenol, or naphthenic acid; the metal compound is calcium oxide, calcium hydroxide, or magnesium oxide; the promoter is methanol, ethanol, or butanol; the solvent is solvent gasoline, toluene, or xylene; and the auxiliary agent is formic acid, acetic acid, or ammonia water.

[0012] In step 2, the non-ionic surfactant is fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, or coconut oil monoethanolamide.

[0013] In step 2, the frequency of the ultrasonic device is 2k Hz-60k Hz; and the free base value is 10-60mgKOH / g.

[0014] The mass ratio of the oil-soluble organic acid, the lubricating oil base oil, the metal compound, the non-ionic surfactant, the promoter, the auxiliary agent, and the solvent is 70-120:70-120:1-50:20-150:10-100:0.1-10:10-300.

[0015] In steps 2 and 3, when the solvent is removed, the temperature is raised to 100℃-170℃.

[0016] In step 3, the solvent is solvent gasoline, toluene, or xylene.

[0017] The present application has the following beneficial effects: by combining anionic surfactants with non-ionic surfactants and using ultrasonic technology to prepare the metal detergent, the stability of the metal detergent to water, methanol, etc. is effectively improved, and the mass transfer, heat transfer, and other dispersion problems among the gas, solid, and liquid phases in the preparation process are solved, and the synthesized metal detergent has water and methanol resistance stability. DETAILED DESCRIPTION

[0018] The present application will be described in detail below in conjunction with specific embodiments.

[0019] The method for preparing the metal detergent using ultrasonic waves according to the present application is implemented according to the following steps:

[0020] Step 1, mixing and stirring the oil-soluble organic acid, lubricating oil base oil, metal compound, promoter, auxiliary agent, solvent, carrying out neutralization reaction to obtain anionic surfactant mixture;

[0021] The neutralization reaction temperature is 40-100℃, and the reaction time is 0.5h;

[0022] The oil-soluble organic acid is any one or more of alkyl benzene sulfonic acid, alkyl salicylic acid, sulfated alkyl phenol, naphthenic acid;

[0023] The lubricating oil base oil is a kind of base oil, a kind of synthetic oil, a kind of synthetic oil, a kind of synthetic oil, a kind of synthetic oil, preferably HVI 150;

[0024] The metal compound is calcium oxide, calcium hydroxide or magnesium oxide; the promoter is methanol, ethanol or butanol; the solvent is solvent gasoline, toluene or xylene; the auxiliary agent is formic acid, acetic acid or ammonia water;

[0025] Step 2, under the condition of 30℃-60℃, the nonionic surfactant is added to the anionic surfactant mixture of step 1, the ultrasonic device is started, the nonionic surfactant mixture is obtained, then the carbon dioxide is introduced to a certain free base value, the carbon dioxide is stopped and the ultrasonic device is closed, the temperature is raised to 100℃-170℃ to remove the solvent, auxiliary agent and water, and the crude product is obtained.

[0026] The nonionic surfactant is fatty alcohol polyoxyethylene ether, nonyl phenol polyoxyethylene ether or coconut oil monoethanol amide;

[0027] The frequency of the ultrasonic device is 2k Hz-60k Hz;

[0028] The controlled free base value (DBN) is 10-60mgKOH / g;

[0029] The mass ratio of oil-soluble organic acid, lubricating oil base oil, metal compound, nonionic surfactant, promoter, auxiliary agent, solvent is 70-120:70-120:1-50:20-150:10-100:0.1-10:10-300;

[0030] Step 3, adding solvent to dilute the crude product, removing solid residue by centrifugation to obtain filtrate, raising the temperature to 100℃-170℃ to remove the solvent, and obtaining metal detergent;

[0031] The solvent is solvent gasoline, toluene or xylene;

[0032] The present application solves the stability problem of metal cleaning agent to water, methanol and the like by means of combination of anionic surfactant and nonionic surfactant; and solves the dispersion problem of mass transfer, heat transfer and the like among three phases of gas, solid and liquid of anionic surfactant, nonionic surfactant, metal oxide and carbon dioxide in the preparation process of metal cleaning agent by means of ultrasonic technology.

[0033] Example 1

[0034] At normal temperature, 100 mL of straight-run gasoline, 50 g of alkyl salicylic acid, 50 g of base oil, 30 g of calcium hydroxide and 15 g of methanol were added into a 500 mL three-necked flask with a stirrer, and stirred, and neutralization reaction was carried out at 50℃ for 30 min; then ultrasonic radiation conditions were set, 10 g of fatty alcohol polyoxyethylene ether (AEO-3) was added at a temperature of 50℃, an ultrasonic power of 350 W and a frequency of 60 kHz, carbon dioxide gas was introduced at a rate of 150 mL / min, and high alkalinity reaction was carried out for 3 h. After the reaction was completed, the temperature was raised to 110℃, water and methanol were removed by distillation, and then the temperature was lowered, gasoline was added for dilution, sedimentation and centrifugation (filtration) to remove slag, and then the solvent was removed by distillation to obtain the product metal cleaning agent.

[0035] Example 2

[0036] At normal temperature, 100 mL of straight-run gasoline, 50 g of alkyl benzene sulfonic acid, 50 g of base oil, 35 g of calcium hydroxide and 15 g of methanol were added into a 500 mL three-necked flask with a stirrer, and stirred, and neutralization reaction was carried out at 50℃ for 30 min; then ultrasonic radiation conditions were set, 10 g of nonylphenol polyoxyethylene ether (NP-4) was added at a temperature of 50℃, an ultrasonic power of 350 W and a frequency of 20 kHz, carbon dioxide gas was introduced at a rate of 150 mL / min, and high alkalinity reaction was carried out for 3 h. After the reaction was completed, the temperature was raised to 110℃, water and methanol were removed by distillation, and then the temperature was lowered, gasoline was added for dilution, sedimentation and centrifugation (filtration) to remove slag, and then the solvent was removed by distillation to obtain the product metal cleaning agent.

[0037] Example 3

[0038] At room temperature, a 500 mL three-necked flask with a stirrer was charged with xylene 100 mL, alkyl benzene sulfonic acid 50 g, alkyl salicylic acid 5 g, base oil 50 g, magnesium oxide 27 g, ammonia water 10 g, water 10 g, methanol 15 g, stirred, and neutralization reaction was carried out at 50°C for 30 min. Then, under the condition of ultrasonic radiation, at a temperature of 50°C, an ultrasonic power of 350 W, and a frequency of 35 kHz, coconut fatty acid monoethanolamide (HM800) 10 g was added, carbon dioxide gas was introduced at a rate of 150 mL / min, and high alkalinity reaction was carried out for 5 h. After the reaction was completed, the temperature was raised to 110°C, water and methanol were distilled off, and after cooling, gasoline was added for dilution, sedimentation, centrifugation (filtration) to remove slag, and then the solvent was distilled off to obtain the product metal detergent.

[0039] Example 4

[0040] In a 500 mL four-necked flask, dodecyl phenol 100 g, 150N base oil 100 g, sulfur 18 g, calcium oxide 15 g were added, and the temperature was raised to 155°C. Ethylene glycol 20 g was added dropwise as a promoter, and after the dropwise addition was completed, it was maintained at 140°C for 5 h. Then, under the condition of ultrasonic radiation, at a temperature of 50°C, an ultrasonic power of 350 W, and a frequency of 100 kHz, 10 g of coconut fatty acid monoethanolamide (HM800) and 20 g of calcium oxide were added, and 22 g of carbon dioxide gas was introduced. Then, 10 g of diatomite filter aid was added after cooling, and the filtrate was distilled to remove the solvent to obtain the sulfided calcium alkyl phenate detergent.

[0041] Comparative Example 1

[0042] At room temperature, a 500 mL three-necked flask with a stirrer was charged with straight-run gasoline 100 mL, alkyl salicylic acid 50 g, base oil 50 g, calcium hydroxide 35 g, methanol 15 g, and stirred for neutralization reaction for 30 min, maintaining the temperature at 50°C.

[0043] Carbon dioxide gas was introduced at a temperature of 50°C at a rate of 150 mL / min, and high alkalinity reaction was carried out for 3 h. After the reaction was completed, the temperature was raised to 110°C, water and methanol were distilled off, and after cooling, gasoline was added for dilution, sedimentation, centrifugation (filtration) to remove slag, and then the solvent was distilled off to obtain the product detergent.

[0044] Comparative Example 2

[0045] At room temperature, a 500 mL three-necked flask with a stirrer was charged with xylene 100 mL, alkyl benzene sulfonic acid 50 g, alkyl salicylic acid 5 g, base oil 50 g, magnesium oxide 18 g, ammonia water 10 g, water 10 g, methanol 15 g, and stirred for neutralization reaction for 30 min, maintaining the temperature at 50°C.

[0046] The high alkalinity reaction was carried out at 50℃ for 5h with the carbon dioxide gas at a rate of 150mL / min. After the reaction, the temperature was raised to 110℃, and water and methanol were evaporated. After cooling, gasoline was added for dilution, sedimentation, centrifugation (filtration) to remove slag, and then the solvent was removed by distillation to obtain the product detergent.

[0047] Table 1 Product performance test results of examples and comparative examples

[0048]

[0049] The performance detection methods are as follows: alkalinity SH / T 025 "Determination of Alkalinity of Oil Products (High Chloric Acid Potential Titration)"; yield is the mass ratio of product to crude product; storage stability is diluted with lubricating oil base oil at a proportion of 10%, and then left for 3 months; and oil-water separation test is SH / T 0619-95 determination of water separation performance of oil sample.

[0050] As can be seen from Table 1, the yield of the examples is significantly improved compared with the comparative examples, which is due to the application of ultrasonic technology; the oil layer of the oil-water separation test is clear, while the comparative sample is turbid, and the volume of water is significantly less, which shows excellent stability to water, indicating that the combination of anionic and non-ionic surfactants significantly improves the stability of the product to polar non-oil soluble substances.

Claims

1. A method for preparing metal cleaning agents using ultrasonic methods, characterized in that, The specific steps are as follows: Step 1: Mix and stir oil-soluble organic acid, lubricating oil base oil, metal compound, accelerator, additive, and solvent to carry out a neutralization reaction and obtain anionic surfactant mixture; Step 2: Under conditions of 30℃~60℃, add the nonionic surfactant to the anionic surfactant mixture from Step 1, start the ultrasonic device to obtain the nonionic surfactant mixture, then introduce carbon dioxide to a certain free alkalinity, stop introducing carbon dioxide and turn off the ultrasonic device, raise the temperature to remove the solvent, additives and water, and obtain the crude product. The nonionic surfactant is fatty alcohol polyoxyethylene ether AEO-3, nonylphenol polyoxyethylene ether NP-4, or coconut oil monoethanolamide HM800; the frequency of the ultrasonic device is 2kHz ~ 60kHz; the free alkalinity is 10~60 mgKOH / g. The mass ratio of oil-soluble organic acids, lubricating oil base oils, metal compounds, nonionic surfactants, accelerators, additives, and solvents is 70~120:70~120:1-50:20~150:10~100:0.1-10:10~300; Step 3: Add solvent to the crude product for dilution, remove solid residue by centrifugation, obtain filtrate, heat to remove solvent, and obtain metal cleaning agent.

2. The method for preparing a metal cleaning agent using ultrasound according to claim 1, characterized in that, In step 1, the neutralization reaction temperature is 40-100℃ and the reaction time is 0.5h.

3. The method for preparing a metal cleaning agent using ultrasound according to claim 1, characterized in that, In step 1, the oil-soluble organic acid is any one or more of alkylbenzene sulfonic acid, alkyl salicylic acid, sulfide alkylphenol, and naphthenic acid; the metal compound is calcium oxide, calcium hydroxide, or magnesium oxide; the accelerator is methanol, ethanol, or butanol; the solvent is solvent gasoline, toluene, or xylene; and the auxiliary agent is formic acid, acetic acid, or ammonia.

4. The method for preparing a metal cleaning agent using ultrasound according to claim 1, characterized in that, In steps 2 and 3, during solvent removal, the temperature is raised to 100℃~170℃.

5. The method for preparing a metal cleaning agent using ultrasound according to claim 1, characterized in that, In step 3, the solvent is solvent gasoline, toluene, or xylene.

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