Method for preparing metal detergent by using ultrasonic method

Abstract

The invention discloses a method for preparing a metal detergent by using an ultrasonic method, which specifically comprises the following steps: mixing oil-soluble organic acid, lubricant base oil, a metal compound, an accelerant, an auxiliary agent and a solvent, and carrying out neutralization reaction to obtain a mixed solution; adding a nonionic surfactant into the mixed solution, starting an ultrasonic device, introducing carbon dioxide to a certain free alkali value, stopping introducing carbon dioxide, closing the ultrasonic device, and removing the solvent, the auxiliary agent and water to obtain a crude product; and adding a solvent into the crude product for dilution and centrifugation to obtain a filtrate, and removing the solvent to obtain the metal detergent. By combining the anionic surfactant and the nonionic surfactant, the stability problem of the metal detergent to water, methanol and the like is solved; through an ultrasonic technology, the dispersion problems of mass transfer, heat transfer and the like among gas, solid and liquid phases of an anionic surfactant, a nonionic surfactant, a metal oxide, carbon dioxide and the like in the preparation process of the metal detergent are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating oil detergents, and in particular relates to a method for preparing a metal detergent by utilizing an ultrasonic method. Background Art

[0002] Clean energy engines use fuels such as natural gas, methanol, hydrogen, and ammonia to generate power. Compared with gasoline engines and diesel engines, they have cleaner emissions and less pollution. The polar harmful substances such as water, alcohol, and acid produced by the combustion of clean fuel engines seriously damage the lubrication system, causing the acid neutralization ability of lubricating oil to decrease, the base value to drop sharply, and the decomposition of antioxidants and anti-wear agents to accelerate. At the same time, the additives in the lubricating oil are layered into floccules to form sludge precipitation. Existing solutions mainly focus on the formulation optimization of lubricating oils. For example, a Chinese patent (publication number is CN113322119B) discloses a special nano energy-saving lubricating oil for methanol engines and a preparation method thereof, which introduces a multifunctional nano additive-dialkyl dithiophosphoric acid modified zinc oxide nanoparticles and a high-temperature antioxidant to solve the problem of easy oxidation and acidification of methanol engine lubricating oil.

[0003] Metal detergents are the main lubricant additives that have the properties of acid neutralization, alkalinity retention and certain anti-wear properties. Therefore, it is critical to improve the metal detergent's resistance to polar harmful substances such as water, alcohol, and acid. Common metal detergents are generally anionic soap surfactants formed by organic acids and their combinations, such as different combinations of different anionic surfactants such as calcium alkylbenzene sulfonate, calcium alkyl salicylate, calcium sulfide alkylphenol, calcium cyclohexane acid, and calcium stearate. However, the anionic surfactants and their compounding cannot solve the problems of decreased acid neutralization ability, sudden drop in alkalinity, and stratification of additives into flocs caused by polar substances such as water, alcohol, and acid. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a metal detergent by using an ultrasonic method, thereby improving the yield and stability of the metal detergent.

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

[0006] Step 1, mixing and stirring an oil-soluble organic acid, a lubricating oil base oil, a metal compound, a promoter, an additive, and a solvent, and performing a neutralization reaction to obtain an anionic surfactant mixed solution;

[0007] Step 2, adding a nonionic surfactant to the anionic surfactant mixed solution of step 1 at 30° C. to 60° C., starting an ultrasonic device to obtain a nonionic surfactant mixed solution, then introducing carbon dioxide to a certain free base value, stopping the introduction of carbon dioxide and turning off the ultrasonic device, raising the temperature to remove the solvent, additives and water to obtain a crude product;

[0008] Step 3, adding a solvent to the crude product for dilution, removing solid residue by centrifugation to obtain a filtrate, and removing the solvent by heating to obtain a metal cleaner.

[0009] The present invention is also characterized in that:

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

[0011] In step 1, the oil-soluble organic acid is any one or more of alkylbenzene sulfonic acid, alkyl salicylic acid, sulfide alkylphenol, and cyclohexane 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 nonionic surfactant is fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether or coconut acid monoethanolamide.

[0013] In step 2, the frequency of the ultrasonic device is 2kHz to 60kHz; and the free alkali value is 10 to 60mgKOH / g.

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

[0015] In step 2 and step 3, when removing the solvent, the temperature is raised to 100°C to 170°C.

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

[0017] The beneficial effects of the present invention are as follows: by combining anionic surfactants with nonionic surfactants and adopting ultrasonic technology to prepare metal detergents, the stability of metal detergents to water, methanol, etc. is effectively improved, and the dispersion problems such as mass transfer and heat transfer between gas, solid and liquid phases in the preparation process are solved. The synthesized metal detergent has water resistance and methanol resistance stability. DETAILED DESCRIPTION

[0018] The present invention is described in detail below in conjunction with specific implementation modes.

[0019] The method for preparing a metal detergent by ultrasonic method of the present invention is specifically implemented according to the following steps:

[0020] Step 1, mixing and stirring an oil-soluble organic acid, a lubricating oil base oil, a metal compound, a promoter, an additive, and a solvent, and performing a neutralization reaction to obtain an anionic surfactant mixed solution;

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

[0022] The oil-soluble organic acid is any one or more of alkylbenzenesulfonic acid, alkylsalicylic acid, sulfonated alkylphenol, and cyclohexane acid;

[0023] The lubricating oil base oil is a Class I base oil, a Class II base oil, a Class III base oil, a Class I synthetic oil, a Class II synthetic oil, a Class III 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°C to 60°C, adding a nonionic surfactant to the anionic surfactant mixed solution of step 1, starting an ultrasonic device to obtain a nonionic surfactant mixed solution, then introducing carbon dioxide to a certain free base value, stopping the introduction of carbon dioxide and turning off the ultrasonic device, raising the temperature to 100°C to 170°C to remove the solvent, additives and water, and obtaining a crude product.

[0026] The nonionic surfactant is fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether or coconut acid monoethanolamide;

[0027] The frequency of the ultrasonic device is 2 kHz to 60 kHz;

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

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

[0030] Step 3, adding a solvent to the crude product for dilution, removing solid residue by centrifugation to obtain a filtrate, heating to 100° C. to 170° C. to remove the solvent, and obtaining a metal detergent;

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

[0032] The present invention solves the stability problem of metal detergents to water, methanol, etc. by combining anionic surfactants with nonionic surfactants; and solves the dispersion problems of mass transfer, heat transfer, etc. among gas, solid, and liquid phases such as anionic surfactants and nonionic surfactants, metal oxides, and carbon dioxide during the preparation of metal detergents by ultrasonic technology.

[0033] Example 1

[0034] At room temperature, add 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 to a 500 mL three-necked flask with a stirrer, stir, and neutralize for 30 min at 50 ° C; then set the ultrasonic radiation conditions, add 10 g of fatty alcohol polyoxyethylene ether (AEO-3) under the conditions of temperature of 50 ° C, ultrasonic power of 350 W and frequency of 60 kHz, pass carbon dioxide gas, and the ventilation rate is 150 mL / min, and the high alkalinity reaction is carried out for 3 hours. After the reaction is completed, the temperature is raised to 110 ° C, water and methanol are evaporated, and gasoline is added after cooling for dilution, sedimentation, centrifugation (filtration) to remove slag, and then distillation to remove the solvent to obtain the product metal purifier.

[0035] Example 2

[0036] At room temperature, add 100 mL of straight-run gasoline, 50 g of alkylbenzene sulfonic acid, 50 g of base oil, 35 g of calcium hydroxide, and 15 g of methanol to a 500 mL three-necked flask with a stirrer, stir, and neutralize for 30 minutes at 50°C; then set the ultrasonic radiation conditions, add 10 g of nonylphenol polyoxyethylene ether (NP-4) under the conditions of temperature of 50°C, ultrasonic power of 350 W and frequency of 20 kHz, pass carbon dioxide gas, and the ventilation rate is 150 mL / min, and carry out high alkalinity reaction for 3 hours. After the reaction is completed, the temperature is raised to 110°C, water and methanol are evaporated, gasoline is added after cooling, and the product metal purifier is obtained by dilution, sedimentation, centrifugation (filtration) and slag removal, and then distillation and removal of solvent.

[0037] Example 3

[0038] At room temperature, add 100mL of xylene, 50g of alkylbenzene sulfonic acid, 5g of alkyl salicylic acid, 50g of base oil, 27g of magnesium oxide, 10g of ammonia water, 10g of water, and 15g of methanol to a 500mL three-necked flask with a stirrer, stir, and neutralize for 30min at 50°C. Then set the ultrasonic radiation conditions, add 10g of coconut oil monoethanolamide (HM800) under the conditions of temperature of 50°C, ultrasonic power of 350W and frequency of 35kHz, pass carbon dioxide gas, and the ventilation rate is 150mL / min, and the high alkalinity reaction is carried out for 5h. After the reaction is completed, the temperature is raised to 110°C, water and methanol are evaporated, gasoline is added after cooling, dilution, sedimentation, centrifugation (filtration) and slag removal, and then distillation and removal of solvent are carried out to obtain the product metal purifier.

[0039] Example 4

[0040] Add 100g of dodecylphenol, 100g of 150N base oil, 18g of sulfur, and 15g of calcium oxide to a 500mL four-necked bottle, raise the temperature to 155°C, drop 20g of ethylene glycol as a promoter, and keep the temperature at 140°C for 5 hours after the dropwise addition is completed; then set the ultrasonic radiation conditions, add 10g of coconut oil monoethanolamide (HM800) and 20g of calcium oxide under the conditions of temperature of 50°C, ultrasonic power of 350W and frequency of 100KHz, and fill in 22g of carbon dioxide gas. Then cool down, add 10g of diatomaceous earth filter aid, filter, and distill the filtrate to remove the solvent to obtain the sulfurized alkylphenol calcium detergent.

[0041] Comparative Example 1

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

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

[0044] Comparative Example 2

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

[0046] At a temperature of 50°C, carbon dioxide gas was introduced at a ventilation rate of 150 mL / min, and the high alkalinity reaction was carried out for 5 hours. After the reaction was completed, the temperature was raised to 110°C, water and methanol were evaporated, gasoline was added after cooling, dilution, sedimentation, centrifugation (filtration) to remove slag, and then distillation to remove the solvent to obtain the product detergent.

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

[0048]

[0049] The performance testing methods are as follows: base value SH / T 025 "Determination of base value of oil products (perchloric acid potentiometric titration method)"; the yield is the mass ratio of the product to the crude product; the storage stability is diluted with lubricating oil base oil at a ratio of 10% and left to stand for 3 months; the oil-water separation test is SH / T 0619-95 to determine the water separation performance of the oil sample.

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

Claims

1. A method for preparing a metal detergent using an ultrasonic method, characterized in that: Follow the steps below to implement it: Step 1, mixing and stirring an oil-soluble organic acid, a lubricating oil base oil, a metal compound, a promoter, an additive, and a solvent, and performing a neutralization reaction to obtain an anionic surfactant mixed solution; Step 2, adding a nonionic surfactant to the anionic surfactant mixed solution of step 1 at 30° C. to 60° C., starting an ultrasonic device to obtain a nonionic surfactant mixed solution, then introducing carbon dioxide to a certain free base value, stopping the introduction of carbon dioxide and turning off the ultrasonic device, raising the temperature to remove the solvent, additives and water to obtain a crude product; Step 3, adding a solvent to the crude product for dilution, removing solid residue by centrifugation to obtain a filtrate, and removing the solvent by heating to obtain a metal cleaner.

2. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: In the step 1, the neutralization reaction temperature is 40-100° C., and the reaction time is 0.5 h.

3. The method for preparing a metal detergent by ultrasonic method 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 cyclohexane 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.

4. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: In the step 2, the nonionic surfactant is fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether or coconut acid monoethanolamide.

5. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: In the step 2, the frequency of the ultrasonic device is 2kHz to 60kHz; and the free alkali value is 10 to 60mgKOH / g.

6. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: The mass ratio of oil-soluble organic acid, lubricating oil base oil, metal compound, non-ionic surfactant: accelerator, auxiliary agent and solvent is 70-120:70-120:1-50:20-150:10-100:0.1-10:10-300.

7. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: In the step 2 and step 3, when removing the solvent, the temperature is raised to 100° C. to 170° C.

8. The method for preparing a metal detergent by using an ultrasonic method according to claim 1, characterized in that: In step 3, the solvent is solvent gasoline, toluene or xylene.

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