CN113322119B - Special nano energy-saving lubricating oil for methanol engine and preparation method thereof - Google Patents
Special nano energy-saving lubricating oil for methanol engine and preparation method thereof Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
Abstract
The invention discloses a special nano energy-saving lubricating oil for a methanol engine, which comprises the following components in parts by weight: 88-90 parts of base oil, 9011 parts of an antifoaming agent T9011 parts, 6021-2 parts of a viscosity agent T6021, 106D 1-2 parts of a detergent T106, 1511-2 parts of a dispersant T, 21-2 parts of an antioxidant T5121, 1-2 parts of a high-temperature antioxidant A and 2-3 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles. The invention introduces a multifunctional nano additive, namely dialkyl dithiophosphate modified zinc oxide nano particles and a high-temperature antioxidant A to solve the problem that the lubricating oil of a methanol engine is easy to oxidize and acidify. The novel lubricating oil formula overcomes the problems of corrosive wear, easy layering of lubricating oil, oxidation and acidification and the like caused by methanol combustion on an engine, can keep the dispersion stability of the engine for a long time, and greatly prolongs the service life of the lubricating oil and the service life of novel engine parts.
Description
Technical Field
The invention belongs to the technical field of lubricating oil, and particularly relates to special nano energy-saving lubricating oil for a methanol engine and a preparation method thereof.
Background
The methanol is used as a clean fuel and has important significance for solving the problem of atmospheric pollution caused by automobile exhaust emission and relieving the shortage of petroleum resources. In 2019, eight committees such as the Ministry of industry and communications and the department of science and technology of China jointly come out guidance on the development of methanol automobile applications in partial regions, and specific guidance suggestions are provided for the industrial development of methanol automobiles. The working condition and the combustion by-products of the methanol automobile engine are greatly different from those of the traditional gasoline and diesel engines, so that the requirements on lubricating oil are different. However, mature special lubricating oil for methanol engines is lacked at home and abroad at present, and the development of the special lubricating oil is an urgent need of the industry. Methanol gasoline easily generates substances such as formaldehyde, formic acid and the like in the combustion process, on one hand, the methanol gasoline is easily adsorbed on the surface of a friction pair of an engine to aggravate the corrosion and the abrasion of the engine, and on the other hand, the methanol gasoline can quickly reduce alkali reserves in lubricating oil to accelerate the oxidation and acidification of the lubricating oil. Meanwhile, the methanol in the fuel oil stratifies the additives in the lubricating oil into floccules to form sludge sediment.
At present, aiming at the problem of corrosion and abrasion of methanol engine parts, a large number of non-metal wear-resistant and corrosion-resistant parts are applied to methanol engines, including nitriding, DLC carbon film coatings, silicon-aluminum alloy substrates and other friction auxiliary materials, but currently developed engine lubricating oil is still developed aiming at metal surfaces, particularly, friction-reducing and wear-resistant agents are mostly compounds containing sulfur and phosphorus elements, and the working mechanism of the friction-reducing and wear-resistant agents is based on the friction chemical reaction with the metal surfaces of the engine materials to form metal compound friction films with friction-reducing or wear-resistant functions. Aiming at the non-metal surface, the mechanisms can not be realized, so that the service time and the stability of the non-metal friction pair are greatly reduced, and the advantage of the methanol engine can not be realized.
Therefore, in order to better popularize methanol gasoline, three problems of good wear resistance, delamination resistance and oxidation resistance of the methanol gasoline engine lubricating oil must be solved. A targeted lubricating oil is needed to make up for the deficiency of the current dedicated lubricating oil for methanol engines.
Disclosure of Invention
Aiming at three problems of wear resistance, delamination resistance and oxidation resistance of the lubricating oil of the methanol gasoline engine, the invention provides an optimized formula of the special nano energy-saving lubricating oil for the methanol engine, which realizes the functional requirements of stable dispersion of dihydroxydithiophosphoric acid modified zinc oxide nano particles, synergetic oxidation resistance, lubrication and the like, solves the problem of wear caused by mismatching of the friction pair of the existing lubricating oil and the methanol engine, solves the problem of easy oxidation and acidification of the lubricating oil of the methanol engine by using a high-temperature resistant phenolic amine dual-function antioxidant, and improves the delamination resistance by optimized combination of base oil, a dispersing agent and a cleaning agent.
The invention also provides a preparation method of the special nano energy-saving lubricating oil for the methanol engine.
In order to achieve the purpose, the invention adopts the following technical scheme:
a special nanometer energy-saving lubricating oil for a methanol engine comprises the following components in parts by weight: 88-90 parts of base oil, 9011 parts of an antifoaming agent T9011 parts, 6021-2 parts of a viscosity agent T6021, 106D 1-2 parts of a detergent T106, 1511-2 parts of a dispersant T, 21-2 parts of an antioxidant T5121, 1-2 parts of a high-temperature antioxidant A and 2-3 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
The adhesive T602 is a viscosity index improver T602, of the polymethacrylate type (PMA).
The high-temperature antioxidant A is prepared by referring to Chinese patent CN105038904A (CN 201510415002.1, a high-temperature antioxidant for lubricating oil and a preparation method thereof), 2, 6-di-tert-butylphenol and substituted diphenylamine are used as raw materials, n-decane is used as a high-boiling point solvent, the reaction is carried out for 2 to 4 hours at the temperature of 120-170 ℃ under the action of a catalyst and in an inert gas atmosphere, and a target product is obtained by post-treatment of the product. The substituted diphenylamine is mono-substituted or multi-substituted diphenylamine in ortho-, para-or meta-substitution, and the substituent is an alkyl or alkoxy substituent with 1-9 carbon atoms, including a straight-chain substituent and a branched-chain substituent.
The dialkyl dithiophosphate modified zinc oxide nanoparticles are prepared according to Chinese patent CN110129110A (CN 201910456608.8, a dialkyl dithiophosphate modified zinc oxide nanoparticles and a preparation method and application thereof). The method comprises the steps of adding an alcohol solution of inorganic strong base or organic strong base into a polar organic solvent of zinc dialkyl dithiophosphate, reacting for 10-14 h at 30-40 ℃, removing the solvent after the reaction is finished, and then washing and drying to obtain the dialkyl dithiophosphate modified zinc oxide nanoparticles. The hydrocarbyl group in the dihydrocarbyl dithiophosphoric acid is a primary alkyl group, a secondary alkyl group or an aryl group having 4 to 22 carbon atoms.
Further, the base oil is blended by 150SN, 200N, 100N, 500SN and 150BS to reach the required viscosity grade, for example, the base oil can be blended by 100N and 150SN to be base oil with the viscosity grades of 0W20, 5W30 and 5W40 respectively.
Further preferably, the lubricating oil comprises the following components in parts by weight: 88 parts of base oil, 9011 parts of anti-foaming agent T, 6022 parts of adhesive agent T6022 parts of detergent T106D 2 parts, 1512 parts of dispersant T, 5121 parts of antioxidant T, 2 parts of high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
Further preferably, the lubricating oil comprises the following components in parts by weight: 89 parts of base oil, 9011 parts of an antifoaming agent, 6021 parts of a viscosity agent T6021 part, 106D 2 parts of a detergent T106, 1512 parts of a dispersant T, 5121 parts of an antioxidant T, 2 parts of a high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
Further preferably, the lubricating oil comprises the following components in parts by weight: 90 parts of base oil, 9011 parts of an antifoaming agent, 6021 parts of a viscosity-indicating agent T6021 part, 106D 2 parts of a detergent T106, 1511 parts of a dispersant T, 5121 parts of an antioxidant T, 2 parts of a high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
The invention provides a preparation method of the special nano energy-saving lubricating oil for the methanol engine, which specifically comprises the following steps:
1) sequentially adding part (such as 1/5) of base oil, a dispersant T151 and dialkyl dithiophosphoric acid modified zinc oxide nanoparticles into a mixing reaction kettle, stirring at the speed of 150-250 r/min for 1-2h, and then carrying out ultrasonic treatment on the sample in the kettle for 20-30 min by using an ultrasonic dispersion probe to uniformly disperse to obtain dialkyl dithiophosphoric acid modified zinc oxide nanoparticle dispersion liquid;
2) and (3) adding the rest base oil, the antifoaming agent T901, the finger-sticking agent T602, the detergent T106D, the antioxidant T512 and the high-temperature antioxidant A into the dispersion liquid in sequence, stirring and reacting for 3-4 h at the speed of 300-400 r/min under the condition of normal temperature and normal pressure, and standing to obtain the finished oil. Sampling, inspecting and analyzing, and pumping and filling after the product is qualified. .
The raw materials (except the dialkyl dithiophosphate modified zinc oxide nanoparticles and the high-temperature antioxidant A) used in the special nano energy-saving lubricating oil for the methanol engine are all common commercial products. The dialkyl dithiophosphate modified zinc oxide nanoparticles are prepared according to a patent (ZL 201910456608.8) which is already granted by Henan university. The modifier dialkyl dithiophosphate modifies the zinc oxide nano particles to improve the dispersion stability of the zinc oxide nano cores in the base oil and provide an antioxidant and anticorrosive function. The high temperature antioxidant A was prepared according to the granted patent (ZL 201510415002.1).
The inventor researches and considers that the zinc oxide nanoparticles modified by dialkyl dithiophosphate have strong nucleophilic force on metals and nonmetals, and can overcome the limitation that the traditional anti-wear and anti-friction agent is not suitable for a nonmetallic friction pair. The phenolic amine macromolecular antioxidant effectively improves the antioxidant capacity in the presence of acid and aldehyde. However, because the engine lubricating oil contains various additives to meet the requirements of the engine lubricating oil on functions such as oxidation resistance, dispersion, cleanness, foam resistance, viscosity regulation and the like, the nano additive and the macromolecular antioxidant are optimally compounded with the additives to realize stable dispersion of the nano additive in the lubricating oil, so that the functions of synergetic oxidation resistance, lubrication, viscosity regulation and the like are exerted, and the requirements of the lubricating oil on working conditions of a methanol engine are met.
Compared with the prior art, the invention has the following beneficial effects:
aiming at three problems of wear resistance, delamination resistance and oxidation resistance of the methanol gasoline engine lubricating oil, the invention firstly uses dialkyl dithiophosphoric acid modified zinc oxide nanoparticles (ZL 201910456608.8) as an anti-friction and wear-resistant agent and an antioxidant, and utilizes the zinc oxide nanoparticle inner core to deposit and form an anti-friction film on the surfaces of various metal (cast iron, silicon-aluminum alloy) and nonmetal (nitriding and DLC carbon film) friction pairs so as to achieve the lubrication protection effect on the anti-corrosion friction surface of the methanol engine and overcome the defect that the traditional micromolecular wear-resistant agent needs to generate a friction chemical reaction with a metal substrate to form the anti-friction film (see figure 1). The formula adopts the high-temperature antioxidant A (ZL 201510415002.1) as a main antioxidant, is used as a phenolic amine difunctional macromolecular antioxidant, has high-efficiency antioxidant and high-temperature volatilization decomposition resistance, overcomes the defects that combustion products such as formic acid, formaldehyde and the like degrade the performance of amine antioxidants, inhibits the easy volatilization of phenolic antioxidants, can inhibit the oxidation promotion effect of the combustion products such as formaldehyde, formic acid and the like on lubricating oil in a methanol engine for a long time, has obvious peroxide decomposition capability on a dialkyl dithiophosphate modification layer on the surface of nanoparticles, prevents the continuous proceeding of chain oxidation reaction, and shows outstanding antioxidant capacity compared with the commercially available engine oil in the presence of methanol combustion products (see figure 2). For the delamination of methanol and water and lubricating oil caused in a methanol engine, the invention can realize the stable dispersion of the dialkyl dithiophosphate modified zinc oxide nanoparticles in the engine lubricating oil by optimally screening the anti-delamination capability of the base oil, the dispersant, the detergent and the finger-sticking agent, and simultaneously, the formula is suitable for realizing the functions of oxidation resistance, wear resistance, viscosity regulation and the like under the condition of mixing formaldehyde, formic acid, methanol and water, so as to solve the three problems of wear resistance, delamination resistance and oxidation resistance of the methanol gasoline engine lubricating oil.
Drawings
A, B in FIG. 1 are friction coefficient and wear rate of the lubricating oil and commercially available SN-grade engine oil according to example 4 of the present invention when the four friction pair materials and bearing steel are ground (friction conditions: friction pair diameter 12.7mm GCr15, single stroke 5mm, linear velocity 0.4m/s, load 200N, temperature 120 ℃);
FIG. 2 is a graph of the onset oxidation temperature (A) and oxidation induction time (B) for a lubricating oil according to example 4 of the present invention containing 1.5% formaldehyde and 1% formic acid.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1 Stable Dispersion optimization experiment of Dihydroxydithiophosphate-modified Zinc oxide nanoparticles in lubricating oil
Referring to the preparation method in Chinese patent ZL 201910456608.8, the inventors prepared and obtained dioctyl dithiophosphoric acid modified zinc oxide nanoparticles (i.e. primary alkyl with the hydrocarbon group having 8 carbon atoms). The inventor conducts experiments with different dispersant types to investigate the dispersion stability of the nanoparticles in the lubricating oil, and the specific experimental design and operation are briefly introduced as follows. In the lubricating oil formulations of examples 1 to 3 of the present invention, the dihydrocarbyl dithiophosphate-modified zinc oxide nanoparticles are not limited to dioctyldithiophosphate-modified zinc oxide nanoparticles.
Different kinds of dispersants and dioctyl dithiophosphate modified zinc oxide nanoparticles are dissolved in base oil (base oil with viscosity grade of 5W40 is prepared by 20% of 100N and 80% of 150 SN), ultrasonically dispersed for 20 minutes, kept stand for 24 hours, then centrifuged for 10 minutes at 4000rpm and room temperature, and an ultraviolet visible spectrophotometer is utilized to measure the increase value of the transmittance. The results are shown in Table 1.
TABLE 1 influence of dispersant type on Dispersion stability of Dioctyl dithiophosphoric acid modified Zinc oxide nanoparticles
According to the dispersing agent types in the table 1, the dispersing stability optimization experiment of the dioctyl dithiophosphoric acid modified zinc oxide nano particles finds that: the zinc oxide nanoparticles are compounded with polyamide dispersants (T151, T152, T153, T161, New Xinxiangruifeng New Material Co., Ltd.) and pentaerythritol ester dispersants (T171, Borun additive Co., Ltd., Lanzhou road), wherein the dispersion stability of the dioctyl dithiophosphoric acid modified zinc oxide nanoparticles by the T151 is optimal.
Example 2 Effect of antioxidant species on antioxidant Properties of Formaldehyde and formic acid-containing lubricating oils
After methanol engine combustion products formaldehyde and formic acid are mixed into lubricating oil, the antioxidant capacity of the lubricating oil is obviously deteriorated. When the amine antioxidant commonly used in the traditional antioxidant formula is acidified, the performance of the amine antioxidant is greatly reduced, and the phenolic antioxidant has good antioxidant property in an acid medium but is easy to volatilize. Thus, conventional antioxidant formulations fail to meet the antioxidant requirements of methanol engine lubricating oils. The formula adopts a high-temperature antioxidant A (ZL 201510415002.1) as a main antioxidant, is used as a phenol-amine bifunctional macromolecular antioxidant, has high-efficiency antioxidant and high-temperature volatilization decomposition resistance, can inhibit the oxidation promotion effect of combustion products such as formaldehyde, formic acid and the like on lubricating oil in a methanol engine for a long time, has remarkable peroxide decomposition capability on a dihydroxy dithiophosphate modification layer on the surface of nanoparticles, prevents the continuous proceeding of chain oxidation reaction, and ensures that the lubricating oil still has long-acting antioxidant capability in the presence of formaldehyde and formic acid by compounding with a traditional small molecular additive.
The optimization experiment is judged by measuring the oxidation induction time (the oxidation temperature is controlled at 210 ℃) and the initial oxidation temperature in different antioxidants (T501, T512, T521, T531, T534, New Xinxiangruifeng New Material Co., Ltd.), dioctyl dithiophosphoric acid modified zinc oxide nanoparticles and a high-temperature antioxidant A2, 6-di-tert-butyl-4-diphenylamine based phenol which are compounded and added into base oil (the base oil with the viscosity grade of 5W40 is prepared by 20% of 100N and 80% of 150SN, and 1.5% of formaldehyde and 1% of formic acid are added, wherein the oxidation induction time and the initial oxidation temperature are controlled at 210 ℃).
TABLE 2 antioxidant species and Dioctyl dithiophosphate modified Zinc oxide nanoparticles and high temperature antioxidant for lubricating oils
According to the optimization experiment for analyzing oxidation resistance, the generated acidification environment causes the initial oxidation temperature and the oxidation induction time of the amine antioxidants to be generally inferior to those of the phenolic antioxidants when the methanol combustion product is mixed into the lubricating oil, but the volatility of the phenolic antioxidants causes the amine antioxidants to have poor initial oxidation temperature and oxidation induction timeIts oxidative induction time is limited. The high-temperature antioxidant A shows the optimal antioxidant capacity in the presence of formaldehyde and formic acid (the initial oxidation temperature is 241.3) oCOxidation induction time 22.1 minutes); after the high-temperature antioxidant A and the high-temperature antioxidant T512 are compounded, the oxidation induction time is further prolonged to 37.6 minutes, so that the lubricating oil shows the optimal antioxidant capacity under the working condition of a methanol engine.
Example 3 synergistic optimization experiment of base oil and detergent on formulation resistance to delamination
During the combustion process of the methanol engine, more water and unburned methanol are generated and mixed into lubricating oil, and additives are extracted into methanol and water phase and separated from base oil, so that the lubrication of the engine is failed. The invention ensures that the lubricating oil does not delaminate when the methanol content reaches 50 percent by screening and optimizing the base oil and the detergent. Because ester oil is easy to hydrolyze and is not suitable for methanol engine lubricating oil, the optimized range of the base oil is as follows: group I, II and III, IV oils. Optimization experiments were judged by measuring the 50% methanol stratification tolerance of formulations without detergent compounded with different detergent and base oils. The specific experimental design and operation are briefly introduced as follows:
stirring 40ml base oil and 40ml methanol with a machine to emulsify, preparing two parts, one part at 25 deg.C and the other part at 0 deg.C, and observing layering phenomenon; the results are shown in Table 3, where the delamination ratio is defined as the percentage by volume of methanol after delamination. In table 3, the formulation without detergent is: the anti-foaming agent comprises, by weight, 9011 parts of an anti-foaming agent, 6021 parts of a finger-sticking agent T, 1511 parts of a dispersing agent T, 5121 parts of an antioxidant T, 2 parts of a high-temperature antioxidant A and 2 parts of dioctyl dithiophosphate modified zinc oxide nanoparticles.
TABLE 3 Effect of base oils and detergents on the anti-delamination ability of the formulations
According to the anti-layering emulsification experiment, the high-purity IV-type oil PAO6 with narrow molecular structure distribution has the weakest anti-layering capability and the most stable I-type oil for the base oil. When the I-type oil is compounded with different detergents, the high-base-number synthetic calcium sulfonate has the strongest dispersion stability on methanol, which is related to the fact that a large amount of calcium carbonate inorganic cores have stronger methanol stability. After being compounded with other additives, the lubricating oil containing 50 percent of methanol can be stable and not delaminated at low temperature and room temperature.
Example 4
A special nanometer energy-saving lubricating oil for a methanol engine comprises the following components in parts by weight: 90 parts of base oil (prepared by 20% of 100N and 80% of 150SN into base oil with the viscosity grade of 5W 40), 90 parts of anti-foaming agent T9011 parts, adhesive agent T6021 parts, detergent T106D 2 parts, dispersant T1511 parts, antioxidant T5121 parts, high-temperature antioxidant A (2, 6-di-tert-butyl-4-diphenylamine-phenol) 2 parts and di-N-octyl dithiophosphate modified zinc oxide nano-particles 2 parts.
The preparation method of the special nano energy-saving lubricating oil for the methanol engine specifically comprises the following steps:
1) adding 1/5 base oil, a dispersing agent and di-n-octyl dithiophosphoric acid modified zinc oxide nanoparticles into a blending reaction kettle in sequence, stirring at the speed of 250r/min for 1h, and then dispersing samples in the kettle for 20 min by using an ultrasonic dispersion probe to obtain di-n-octyl dithiophosphoric acid modified zinc oxide nanoparticle dispersion liquid;
2) and (3) adding the rest 4/5 base oil, the anti-foaming agent T901, the finger-sticking agent T602, the detergent T106D, the antioxidant T512 and the high-temperature antioxidant A into the dispersion liquid in sequence, stirring and reacting for 4 hours at the speed of 400r/min under the condition of normal temperature and normal pressure, standing to obtain the finished oil, sampling, inspecting and analyzing, and pumping and filling after the finished oil is qualified.
A, B in FIG. 1 shows the friction coefficient and wear rate of the lubricating oil and commercially available SN-grade engine oil according to example 4 when the four friction pair materials and bearing steel are subjected to friction-to-friction (friction conditions: friction pair diameter 12.7mm GCr15, single stroke 5mm, linear velocity 0.4m/s, load 200N, temperature 120 ℃ C.). FIG. 2 shows the onset oxidation temperature (A) and oxidation induction time (B) for a lubricating oil according to example 4 of the present invention containing 1.5% formaldehyde and 1% formic acid.As can be seen from fig. 1 and 2: the friction coefficients of the lubricating oil prepared by the embodiment on cast iron, silicon-aluminum alloy, nitriding and DLC carbon film friction pairs are respectively 0.078, 0.080, 0.091 and 0.065, and the wear rates are respectively 1.3 x 10-8mm3N-1m-1、1.6*10-8mm3N-1m-1、1.8*10-8mm3N-1m-1、2.3*10-8mm3N-1m-1The initial oxidation temperature was 242.9 ℃ and the oxidation induction time was 37.6 minutes.
The results of fig. 1 show that: the zinc oxide nanometer particle inner core can be used for depositing on the surfaces of various metal (cast iron, silicon-aluminum alloy) and nonmetal (nitriding, DLC carbon film) friction pairs to form an antifriction friction film, so that the lubricating and protecting effects on the anti-corrosion friction surface of a methanol engine are achieved, and the commercially available SN engine oil compounded by the traditional micromolecule antiwear agent does not have effective antiwear and antifriction effects on the four friction pairs.
The results of fig. 2 show that: the high-temperature antioxidant 2, 6-di-tert-butyl-4-diphenylamine-phenol is used as a main antioxidant and a phenol-amine bifunctional macromolecular antioxidant, and has high-efficiency antioxidant and high-temperature volatilization decomposition resistance, so that the degradation of combustion products such as formic acid, formaldehyde and the like on the performance of the amine antioxidant is overcome, the defect of easy volatilization of classified antioxidants is overcome, the oxidation promotion effect of the combustion products such as formaldehyde, formic acid and the like on lubricating oil in a methanol engine can be inhibited for a long time, meanwhile, a dialkyl dithiophosphoric acid modification layer on the surface of nanoparticles has remarkable peroxide decomposition capacity, the continuous proceeding of chain oxidation reaction is prevented, and the antioxidant has remarkable antioxidant capacity compared with the commercially available SN engine oil in the presence of a methanol combustion product.
Example 5
A special nanometer energy-saving lubricating oil for a methanol engine comprises the following components in parts by weight: 88 parts of base oil (prepared by 40% of 100N and 60% of 150SN into base oil with the viscosity grade of 0W 20), 9011 parts of anti-foaming agent T, 6022 parts of adhesive agent T, 106D 2 parts of detergent T106, 1512 parts of dispersant T, T5121 parts of antioxidant T, 2 parts of high-temperature antioxidant (2, 6-di-tert-butyl-4-diphenylamine-phenol) A and 2 parts of di-N-hexyl dithiophosphate modified zinc oxide nano-particles.
The preparation method of the special nano energy-saving lubricating oil for the methanol engine specifically comprises the following steps:
1) adding 1/5 base oil, a dispersing agent T151 and di-n-hexyl dithiophosphoric acid modified zinc oxide nanoparticles into a blending reaction kettle in sequence, stirring at the speed of 200r/min for 1h, and then dispersing samples in the kettle for 20 min by using an ultrasonic dispersion probe to obtain dihexyl dithiophosphoric acid modified zinc oxide nanoparticle dispersion liquid;
2) and (3) adding the rest 4/5 base oil, the anti-foaming agent T901, the finger-sticking agent T602, the detergent T106D, the antioxidant T512 and the high-temperature antioxidant A into the dispersion liquid in sequence, stirring and reacting for 4 hours at the speed of 350r/min under the normal temperature and pressure condition, standing to obtain the finished oil, sampling, inspecting and analyzing, and pumping and filling after the finished oil is qualified.
The friction coefficients of the lubricating oil prepared by the embodiment on cast iron, silicon-aluminum alloy, nitriding and DLC carbon film friction pairs are respectively 0.072, 0.078, 0.089 and 0.060, and the wear rates are respectively 1.0 x 10-8mm3N-1m-1、1.3*10-8mm3N-1m-1、1.8*10-8mm3N-1m-1、2.0*10-8mm3N-1m-1The initial oxidation temperature was 244.1 ℃ and the oxidation induction time was 38.3 minutes.
Example 6
A special nanometer energy-saving lubricating oil for a methanol engine comprises the following components in parts by weight: 89 parts of base oil (base oil prepared by 30% of 100N and 70% of 150SN into 5W30 in viscosity grade), 9011 parts of anti-foaming agent, T6021 parts of adhesive, T106D 2 parts of detergent, T1512 parts of dispersant, T5121 parts of antioxidant, 2 parts of high-temperature antioxidant A (2, 6-di-tert-butyl-4-diphenylamine phenol) and 2 parts of diisooctyl dithiophosphoric acid modified zinc oxide nanoparticles.
The preparation method of the special nano energy-saving lubricating oil for the methanol engine specifically comprises the following steps:
1) adding 1/5 base oil, a dispersing agent T151 and diisooctyl dithiophosphoric acid modified zinc oxide nanoparticles into a blending reaction kettle in sequence, stirring at the speed of 150r/min for 1h, and then dispersing samples in the kettle for 20 min by using an ultrasonic dispersion probe to obtain diisooctyl dithiophosphoric acid modified zinc oxide nanoparticle dispersion liquid;
2) and (3) adding the rest 4/5 base oil, the antifoaming agent T901, the finger-sticking agent T602, the detergent T106D, the antioxidant T512 and the high-temperature antioxidant A into the dispersion liquid in sequence, stirring and reacting for 3 hours at the speed of 300r/min under the normal temperature and pressure condition, standing to obtain the finished oil, sampling, inspecting and analyzing, and pumping and filling after the finished oil is qualified.
The friction coefficients of the lubricating oil prepared by the embodiment on cast iron, silicon-aluminum alloy, nitriding and DLC carbon film friction pairs are respectively 0.074, 0.081, 0.088 and 0.061, and the wear rates are respectively 1.5 to 10-8mm3N-1m-1、1.3*10-8mm3N-1m-1、1.9*10-8mm3N-1m-1、2.2*10-8mm3N-1m-1The initial oxidation temperature was 243.1 ℃ and the oxidation induction time was 37.8 minutes.
In summary, it can be seen that: the invention introduces multifunctional nano additive-dialkyl dithiophosphate modified zinc oxide nano particles as extreme pressure antiwear agents, antioxidants and preservatives for use, and the zinc oxide nano particles can form lubricating films on the surfaces of silicon-aluminum alloy, DLC carbon films, nitriding and other anti-corrosion friction auxiliary materials of various methanol engines, thereby greatly improving the stability and the antifriction and antiwear capacities of the methanol engines. Meanwhile, the problem that the methanol engine lubricating oil is easy to oxidize and acidify is solved by adopting the high-temperature antioxidant A. The novel formula specially used for the methanol engine lubricating oil developed and designed by the invention overcomes the problems of corrosion and abrasion of the engine caused by methanol combustion, easy layering of the lubricating oil, oxidation and acidification and the like, and can keep the dispersion stability of the engine for a long time and greatly prolong the service life of the lubricating oil and novel engine parts.
Claims (5)
1. The special nanometer energy-saving lubricating oil for the methanol engine is characterized by comprising the following components in parts by weight: 88-90 parts of base oil, 9011 parts of an antifoaming agent, T6021-2 parts of a viscosity agent, 106D 1-2 parts of a detergent, T1511-2 parts of a dispersant, T5121-2 parts of an antioxidant, A1-2 parts of a high-temperature antioxidant and 2-3 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles;
the base oil is blended by 150SN, 200N, 100N, 500SN and 150BS to reach the required viscosity grade;
the high-temperature antioxidant A takes 2, 6-di-tert-butylphenol and substituted diphenylamine as raw materials, uses n-decane as a high-boiling point solvent, reacts for 2-4 h at the temperature of 120-170 ℃ under the action of a catalyst and in an inert gas atmosphere, and obtains a target product after the product is subjected to post-treatment; the substituted diphenylamine is mono-substituted or multi-substituted diphenylamine in ortho-, para-or meta-substitution, and the substituent is an alkyl or alkoxy substituent with 1-9 carbon atoms, including a straight-chain substituent and a branched-chain substituent.
2. The special nanometer energy-saving lubricating oil for the methanol engine as claimed in claim 1, wherein the lubricating oil comprises the following components in parts by weight: 88 parts of base oil, 9011 parts of anti-foaming agent T, 6022 parts of adhesive agent T6022 parts of detergent T106D 2 parts, 1512 parts of dispersant T, 5121 parts of antioxidant T, 2 parts of high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
3. The special nanometer energy-saving lubricating oil for the methanol engine as claimed in claim 1, wherein the lubricating oil comprises the following components in parts by weight: 89 parts of base oil, 9011 parts of an antifoaming agent, 6021 parts of a viscosity agent T6021 part, 106D 2 parts of a detergent T106, 1512 parts of a dispersant T, 5121 parts of an antioxidant T, 2 parts of a high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
4. The special nanometer energy-saving lubricating oil for the methanol engine as claimed in claim 1, wherein the lubricating oil comprises the following components in parts by weight: 90 parts of base oil, 9011 parts of an antifoaming agent, 6021 parts of a viscosity-indicating agent T6021 part, 106D 2 parts of a detergent T106, 1511 parts of a dispersant T, 5121 parts of an antioxidant T, 2 parts of a high-temperature antioxidant A and 2 parts of dialkyl dithiophosphate modified zinc oxide nanoparticles.
5. The preparation method of the special nanometer energy-saving lubricating oil for the methanol engine as claimed in any one of claims 1 to 4, is characterized by comprising the following steps:
1) sequentially adding part of base oil, a dispersing agent T151 and dialkyl dithiophosphoric acid modified zinc oxide nanoparticles into a mixing reaction kettle, stirring at the speed of 150-250 r/min for 1-2h, and then ultrasonically dispersing uniformly to obtain dialkyl dithiophosphoric acid modified zinc oxide nanoparticle dispersion liquid;
2) adding the rest base oil, the antifoaming agent T901, the finger-sticking agent T602, the detergent T106D, the antioxidant T512 and the high-temperature antioxidant A into the dispersion liquid, stirring and reacting for 3-4 h at the speed of 300-400 r/min under the condition of normal temperature and normal pressure, and standing to obtain the oil-in-water type anti-foaming agent.
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