Fixed gas engine oil complexing agent, preparation method and engine oil

Abstract

The invention discloses a fixed gas engine oil complexing agent, a preparation method and engine oil, the fixed gas engine oil complexing agent comprises, by mass, 30%-60% of a dispersant, 10%-13% of a clearing agent, 10%-12% of an antioxidant, 3%-5% of an oxidation and corrosion inhibitor, 10%-14% of a liquid multifunctional additive, and the balance base oil; wherein the dispersing agent is polyisobutylene succinimide, the clearing agent is alkyl salicylate, the antioxidant is a phenolic ester type antioxidant, the oxidation and corrosion inhibitor is zinc dialkyl dithiophosphate, and the liquid multifunctional additive is nitrogen-containing sterically hindered phenol. According to the technical scheme, the engine oil not only has good oxidation resistance, can slow down deterioration of oil products in use, but also has dispersing and cleaning capacity, can quickly control acidic oxides, effectively controls generation of the acidic oxides and adverse effects caused by the acidic oxides, and prolongs the oil change period of the engine oil.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating compositions, and in particular to a stationary gas engine oil compound, a preparation method of the stationary gas engine oil compound and a stationary gas engine oil. Background Art

[0002] Stationary gas engines are often exposed to long-term continuous high-load operation in harsh environments, and the gas sources are diverse. Therefore, the efficient operation of stationary gas engines is inseparable from good lubrication protection.

[0003] The working characteristics of stationary gas engines require that gas engine oils have appropriate ash content, excellent antioxidant capacity, and appropriate and sufficient alkali reserves.

[0004] In the prior art, when various gas engine oil compounding components are used in stationary gas engine lubricating oils, there is still room for improvement in the high temperature oxidation resistance, cleaning and dispersing properties, and the ability to control acidic substances of the oils. Summary of the invention

[0005] In view of the above problems, the present invention provides a fixed gas engine oil composite, a preparation method and an engine oil. By introducing a new nitrogen-containing hindered phenol as a multifunctional single agent, the composite not only has good antioxidant ability and can slow down the deterioration of the oil in use, but also has dispersion and cleaning ability, can quickly control acidic oxides to prevent them from further corroding the internal components of the engine or generating deposits. The composite has a simple formula system, and the compatibility of various functional agents is good. It shows excellent antioxidant and alkalinity retention capabilities in API Class I and Class II base oils, effectively controls the generation of acidic oxides and the adverse effects caused by them, and prolongs the oil change period of the engine oil.

[0006] To achieve the above-mentioned object, the present invention provides a stationary gas engine oil compound, which comprises, by mass percentage, 30% to 60% of a dispersant, 10% to 13% of a detergent, 10% to 12% of an antioxidant, 3% to 5% of an antioxidant and an anti-corrosion agent, and 10% to 14% of a liquid multifunctional additive, and the balance is base oil;

[0007] The dispersant is polyisobutylene succinimide, the detergent is alkyl salicylate, the antioxidant is a phenolic ester antioxidant, the antioxidant and anticorrosive agent is disuccinic acid bis(octyl) alkyl zinc salt, and the liquid multifunctional additive is nitrogen-containing hindered phenol.

[0008] In the above technical solution, preferably, the dispersant comprises boronated polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, and the mass ratio of the boronated polyisobutylene succinimide to the high molecular weight polyisobutylene succinimide is (1.5-2.5): (2.5-3.5).

[0009] In the above technical solution, preferably, the N content in the boronated polyisosuccinimide is 1.25%, the boron content is 0.35%, and the N content in the high molecular weight polyisobutylene succinimide is 1.1%.

[0010] In the above technical solution, preferably, the high molecular weight polyisobutylene succinimide is first obtained by reacting high molecular weight polyisobutylene with maleic anhydride to obtain polyisobutylene maleic anhydride, which is then used as a raw material to react with polyamine in different preset proportions to obtain polyisobutylene maleic anhydride.

[0011] In the above technical solution, preferably, the alkyl salicylate is high base calcium salicylate, and the structural formula of the high base calcium salicylate is:

[0012]

[0013] Among them, R1 and R2 are C14-C18, C20-C24, and C24-C28 alkyl groups respectively.

[0014] In the above technical solution, preferably, the structural formula of the phenolic ester antioxidant is:

[0015]

[0016] Wherein, R is a straight chain or branched chain alkyl group having 1 to 12 carbon atoms.

[0017] In the above technical solution, preferably, the structural formula of the nitrogen-containing hindered phenol is:

[0018]

[0019] Wherein, R3 and R4 represent a straight chain or branched chain alkyl group having 1 to 12 carbon atoms respectively.

[0020] In the above technical solution, preferably, the nitrogen-containing hindered phenol is diisooctylamine-hindered phenol, and the structural formula is:

[0021]

[0022] The present invention also provides a method for preparing a stationary gas engine oil compound, which is used to prepare the stationary gas engine oil compound disclosed in any one of the above technical solutions, comprising:

[0023] Adding polyisobutylene succinimide, alkyl salicylate, phenol ester antioxidant and nitrogen-containing hindered phenol into a container in sequence;

[0024] The components in the container are heated to 55-65° C. while stirring, and stirred at 600 rpm for 1 hour;

[0025] Add dioctyl alkyl zinc thiophosphate and base oil at 60-65° C., continue stirring for 2 hours, and filter to obtain the stationary gas engine oil composite.

[0026] The present invention also provides a stationary gas engine oil, which is obtained by mixing a base oil and the stationary gas engine oil composite agent disclosed in any one of the above technical solutions according to a preset ratio.

[0027] Compared with the prior art, the present invention has the following beneficial effects: by introducing a novel nitrogen-containing hindered phenol as a multifunctional single agent, the present invention not only has good antioxidant ability and can slow down the deterioration of the oil in use, but also has dispersing and cleaning ability and can quickly control acidic oxides to prevent them from further corroding the internal components of the engine or generating deposits; the formula system of the composite agent is simple, the compatibility of each functional agent is good, and the composite agent exhibits excellent antioxidant and alkalinity retention abilities in API Class I and Class II base oils, effectively controls the generation of acidic oxides and the adverse effects caused by them, and prolongs the oil change period of the engine oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A schematic diagram of the total base number variation trend of the used engine oil samples compared with Comparative Example 10 and Example 3 of the present invention;

[0029] Figure 2 A schematic diagram of the change trend of the effective base number of the used engine oil samples compared with Comparative Example 10 and Example 3 of the present invention;

[0030] Figure 3 A schematic diagram of the acid value variation trend of the used engine oil samples compared with Comparative Example 10 and Example 3 of the present invention;

[0031] Figure 4 A schematic diagram of the change trend of the oxidation value of the used engine oil samples compared with Comparative Example 10 and Example 3 of the present invention;

[0032] Figure 5 The figure is a schematic diagram of the nitration value variation trend of the used engine oil samples compared with the comparative example 10 and the embodiment 3 of the present invention. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] The present invention is further described in detail below in conjunction with the accompanying drawings:

[0035] A stationary gas engine oil compound provided by the present invention comprises, by mass percentage, 30% to 60% of a dispersant, 10% to 13% of a detergent, 10% to 12% of an antioxidant, 3% to 5% of an antioxidant and an anti-corrosion agent, and 10% to 14% of a liquid multifunctional additive, and the remainder is base oil;

[0036] The dispersant is polyisobutylene succinimide, the detergent is alkyl salicylate, the antioxidant is a phenol ester antioxidant, the antioxidant and anticorrosive agent is dioctyl alkyl zinc thiophosphate, and the liquid multifunctional additive is nitrogen-containing hindered phenol.

[0037] In this embodiment, by introducing a new type of nitrogen-containing hindered phenol as a multifunctional single agent, it not only has good antioxidant ability and can slow down the deterioration of the oil in use, but also has dispersion and cleaning ability, can quickly control acidic oxides to prevent them from further corroding the internal components of the engine or generating deposits, and the formula system of the composite agent is simple, the compatibility of each functional agent is good, and it shows excellent antioxidant and alkalinity retention ability in API Class I and Class II base oils, effectively controls the generation of acidic oxides and the adverse effects caused by them, and prolongs the oil change period of the engine oil.

[0038] In the above embodiment, preferably, the dispersant comprises boronated polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, and the mass ratio of the boronated polyisobutylene succinimide to the high molecular weight polyisobutylene succinimide is (1.5-2.5):(2.5-3.5).

[0039] Specifically, a dispersant is a surfactant composed of an oil-soluble group and a polar group. Its basic functions in lubricating oil include washing, neutralization, solubilization and dispersion. It is mainly a nitrogen-containing polar group or a non-polar chain hydrocarbon group, which interacts with the solid carbon deposits and sludge deposits produced by friction and oxidation during use through molecular interactions, thereby achieving the purpose of controlling the aggregation of solid particles to reform carbon deposits and reducing the degree of sludge.

[0040] In the above embodiment, preferably, the high molecular weight polyisobutylene succinimide is firstly prepared by reacting high molecular weight polyisobutylene with maleic anhydride to obtain polyisobutylene maleic anhydride, which is then used as a raw material to react with polyamine in different preset proportions.

[0041] In the above embodiment, preferably, the N content in the boronated polyisosuccinimide is 1.25%, the boron content is 0.35%, and the N content in the high molecular weight polyisobutylene succinimide is 1.1%.

[0042] Specifically, within a certain range, the higher the nitrogen content of polyisobutylene succinimide, the better its dispersibility; the larger the molecular weight of polyisobutylene and the longer the hydrocarbon chain, the better the oxidation stability of polyisobutylene succinimide. For boronated polyisobutylene succinimide, the boronated ashless dispersant not only has the superior dispersing properties of the dispersant, but also has a promoting effect in terms of anti-wear and anti-oxidation.

[0043] In the above embodiment, preferably, the alkyl salicylate is high base calcium salicylate, and the structural formula of high base calcium salicylate is:

[0044]

[0045] Among them, R1 and R2 are C14-C18, C20-C24, and C24-C28 alkyl groups respectively.

[0046] Specifically, calcium alkyl salicylate is an important lubricating oil detergent, which has a good cleaning effect on top ring grooves and top ring carbon deposits. It uses alkylphenol and calcium hydroxide as initial raw materials, and through the action of a promoter, at a certain temperature and pressure, successively undergoes a neutralization, carboxylation and high-basicity reaction process to obtain high-basicity calcium salicylate. Finally, the product is subjected to subsequent treatment. The ideal target product consists of three parts: neutral soap salt, diluent oil and inorganic alkaline salt. The active parts are the alkaline salt and the neutral soap salt part. The alkaline salt is CaCO3, and the neutral salt is calcium alkyl salicylate. The neutral salt is adsorbed around the alkaline salt to form a colloid dispersed in the diluent oil.

[0047] In the above embodiment, preferably, the structural formula of the phenolic ester antioxidant is:

[0048]

[0049] Wherein, R is a straight chain or branched chain alkyl group having 1 to 12 carbon atoms.

[0050] Specifically, lubricants are oxidatively degraded by heat and oxygen to produce free radicals, which further react with hydrocarbons to produce substances such as alcohols, aldehydes, ketones and water. Antioxidants react with free radicals (the initial rupture products) generated at high temperatures and high pressures, thereby inhibiting the oxidative degradation of lubricants. Excellent phenolic ester antioxidants usually have suitable steric hindrance and high electron delocalization, thus combining high efficiency and durability.

[0051] In the above embodiment, the antioxidant and anti-corrosion agent is a primary alkyl zinc salt of bis-octyl thiophosphate. The antioxidant and anti-corrosion agent is a multi-effect additive with antioxidant, anti-corrosion and anti-wear effects, and is often used as a peroxide decomposer. Primary alkyl zinc salt of bis-octyl thiophosphate is generally not used alone, but is usually used in combination with detergents and dispersants for engine oil. It is worth noting that the phosphorus in ZDDP can poison the precious metal catalyst in the exhaust catalytic converter. In order to avoid catalyst poisoning, high-quality engine oil requires low phosphorus and low ash content.

[0052] In the above embodiment, preferably, the structural formula of the nitrogen-containing hindered phenol is:

[0053]

[0054] Wherein, R3 and R4 represent a straight chain or branched chain alkyl group having 1 to 12 carbon atoms respectively.

[0055] Specifically, hindered phenol improves its antioxidant properties by introducing amino groups. At the same time, it has dispersibility and cleanliness, and through the synergistic effect within the molecule, it achieves a one-dose multi-purpose effect. More importantly, the product is pollution-free.

[0056] In the above embodiment, preferably, the nitrogen-containing hindered phenol is diisooctylamine-hindered phenol, and the structural formula is:

[0057]

[0058] The present invention also provides a method for preparing a stationary gas engine oil compound, which is used to prepare the stationary gas engine oil compound disclosed in any one of the above embodiments, comprising:

[0059] Adding polyisobutylene succinimide, alkyl salicylate, phenol ester antioxidant and nitrogen-containing hindered phenol into a container in sequence;

[0060] The components in the container were heated to 55-65°C while stirring, and stirred at 600 rpm for 1 hour;

[0061] Add dioctyl alkyl zinc thiophosphate and base oil at 60-65° C., continue stirring for 2 hours, and filter to obtain a stationary gas engine oil compound.

[0062] The present invention further provides a stationary gas engine oil, which is obtained by mixing a base oil and the stationary gas engine oil composite disclosed in any one of the above embodiments according to a preset ratio.

[0063] The stationary gas engine oil compound, preparation method and engine oil disclosed in the above embodiments are described using examples and comparative examples during implementation.

[0064] Based on Tables 1 and 2 below, Examples 1-4 and Comparative Examples 1-10 are respectively set, and the API 1509 classification standard is shown in Table 3. The typical single-grade oil formulas configured with Group I base oil and Group II base oil are shown in Table 4 below. After the finished oil is configured according to Table 4, the copper corrosion resistance, oxidation resistance, and high-temperature oxidation resistance and cleaning performance are simulated and evaluated, and a 400-hour engine test is performed.

[0065] Table 1 Component ratio of the embodiment

[0066] Components Example 1 Example 2 Example 3 Example 4 Dispersants 30％ 40％ 50％ 60％ Overbased calcium alkyl salicylate 14％ 13％ 12％ 10％ Phenolic ester antioxidant 12％ 11％ 11％ 10％ Antioxidant and Anticorrosive 3％ 4％ 4％ 5％ Nitrogen-containing hindered phenol 14％ 13％ 12％ 10％ Base oil 27％ 19％ 11％ 5％

[0067] Table 2 Component ratio of comparative example

[0068]

[0069] Table 3 API 1509 base oil classification standards

[0070]

[0071]

[0072] Table 4 Single-grade finished oil formula

[0073] Components SAE 40 Compound 9.0％ Type I base oil (bright oil) 12.0％ Type II base oil 79.0％

[0074] The gas engine oil compound and finished engine oil prepared according to the above-mentioned embodiment were subjected to the following tests to verify the effects.

[0075] (1) High temperature copper corrosion comparison test

[0076] According to SH / T 0754-Diesel engine oil corrosion performance evaluation method at 135℃, the test conditions are 135℃, 168h, and the high temperature copper corrosion of the test samples is tested. The lower the copper rating and the lower the copper content, the better the oil's copper corrosion resistance. The experimental results are shown in Table 5 below:

[0077] Table 5 High temperature copper corrosion test results

[0078]

[0079]

[0080] The power range of stationary gas engines ranges from a few kilowatts to several megawatts, and they are suitable for scenarios of different scales and purposes, and are mainly used for continuous high-load work. Correspondingly, the main shaft and connecting rod of the engine must also bear high loads continuously. This requires that the bearings that match the main shaft and connecting rod must have a higher load-bearing capacity. At present, the mainstream functional layers of bearings are made of bimetallic materials. In addition to aluminum-based alloys, copper-based alloys and lead-based alloys are also common. The most fundamental difference in the quality of lubricants is the extension of the life of the functional layer alloy of the bearing material.

[0081] After simulating the high temperature copper corrosion of the embodiments and comparative examples in the laboratory, it can be concluded from the test results in the above table:

[0082] Examples 1 to 4 and Comparative Examples 4 to 9 contain not only high base value alkyl calcium salicylate, but also a composite dispersant of boronated polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, so that the comprehensive performance of the anti-lead and copper corrosion is better;

[0083] Although Comparative Examples 1 and 2 contain high base value alkyl calcium salicylate, they only use one dispersant, polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, respectively, and their lead and copper corrosion resistance is also reduced, especially the lead corrosion resistance is the worst.

[0084] Although Comparative Example 3 is also a composite dispersant of polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, the detergent is high base calcium sulfonate, and its comprehensive performance against lead and copper corrosion is reduced.

[0085] (2) High temperature oxidation cleanliness comparison test

[0086] According to NB / SH / T 0834—Determination of moderately high temperature piston deposits in engine oil (thermal oxidation simulation test method MHT), the test conditions are 285℃, 24h, and the high temperature oxidation cleanliness of the test sample is tested. The smaller the deposit mass, the better the oil's anti-oxidation cleanliness. The experimental results are shown in Table 6 below:

[0087] Table 6 High temperature oxidation detergency comparison test results

[0088]

[0089]

[0090] The TEOST MHT-4 experimental device was used to evaluate the oxidation detergency in the laboratory. The experimental data in the table show that:

[0091] Examples 1 to 4 and comparative examples 1 to 2 and 4 to 6 contain not only high base value alkyl calcium salicylate, but also a phenolic ester antioxidant and a compound of diisooctylamine-hindered phenol, so that the high temperature oxidation detergency is better.

[0092] Although Comparative Example 3 also contains a phenol ester antioxidant and a compound of diisooctylamine-hindered phenol, the detergent is high-base calcium sulfonate, which leads to a decrease in its high-temperature cleaning performance.

[0093] In Comparative Example 7, diisooctylamine antioxidant was added, and in Comparative Examples 8 to 9, only triisooctylamine and hindered phenol were used, respectively, and their high-temperature detergency was not outstanding.

[0094] (3) Wear resistance comparison test

[0095] According to SH / T 0189 lubricating oil anti-wear performance determination method (four-ball machine method), the anti-wear performance of the samples was evaluated (experimental conditions: 392N, 75°C, 1200r / min, 60min). The experimental results are wear spot diameters. The smaller the wear spot diameter, the better the anti-wear performance of the sample. The specific results are shown in Table 7 below:

[0096] Table 7. Anti-wear comparison test results

[0097]

[0098]

[0099] From the wear data in the table it can be concluded that:

[0100] Examples 1 to 4, Comparative Examples 1 to 3, Comparative Example 5 and Comparative Examples 7 to 9 contain the antioxidant and corrosion inhibitor of bis(octyl) alkyl zinc salt of sulfur and phosphorus, and all exhibit good anti-wear performance.

[0101] Comparative Example 4 uses di-secondary alkyl zinc salt of sulfur and phosphorus, and Comparative Example 6 increases the proportion of di-octyl primary alkyl zinc salt of sulfur and phosphorus, but their anti-wear performance is not ideal. The reason may be that di-octyl primary alkyl zinc salt of sulfur and phosphorus can more easily inhibit the formation of engine paint film, sludge, and ring groove adhesion in gas engines, slow down the wear of cylinders, ring grooves, cams and valve stems, and prevent bearing corrosion.

[0102] (4) Engine test

[0103] According to the internal gas engine test (using harsh experimental conditions: maximum torque), the physical and chemical results of the old oil samples are tracked. The slower the decrease of the base value, the better, indicating that the oil has a better base retention ability; the slower the increase of the acid value, oxidation value and nitration value, the better, indicating that the oil has a better ability to resist oxidation and nitration. The specific results are shown in Table 8 below:

[0104] Table 8 Engine test results

[0105]

[0106]

[0107] Figures 1 to 5 The change trends of the total base number, effective base number, acid number, oxidation number and nitration number of the old engine oil samples compared with Comparative Example 10 and Example 3 are disclosed respectively. Figures 1 to 5 The engine operating data can be obtained:

[0108] Example 3 and Comparative Example 10 maintain the same ratio of high base value alkyl calcium salicylate and the same ratio of di-secondary alkyl zinc thiophosphate, so the sulfate ash of the two is the same. Example 3 introduces diisooctylamine-hindered phenol, which not only improves the effective base value of the oil and enhances the base value retention ability, but also further improves the antioxidant and anti-nitrification properties of the oil, delays the failure process of the engine oil, and extends the oil change cycle.

[0109] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A stationary gas engine oil compound, characterized in that: Calculated by mass percentage, it includes: 30% to 60% of dispersant, 10% to 13% of detergent, 10% to 12% of antioxidant, 3% to 5% of antioxidant and anti-corrosion agent, and 10% to 14% of liquid multifunctional additive, and the balance is base oil; The dispersant is polyisobutylene succinimide, the detergent is alkyl salicylate, the antioxidant is a phenolic ester antioxidant, the antioxidant and anticorrosive agent is disuccinic acid bis(octyl) alkyl zinc salt, and the liquid multifunctional additive is nitrogen-containing hindered phenol.

2. The stationary gas engine oil compound according to claim 1, characterized in that: The dispersant comprises boronated polyisobutylene succinimide and high molecular weight polyisobutylene succinimide, and the mass ratio of the boronated polyisobutylene succinimide to the high molecular weight polyisobutylene succinimide is (1.5-2.5): (2.5-3.5).

3. The stationary gas engine oil compound according to claim 2, characterized in that: The N content of the boronated polyisosuccinimide is 1.25%, the boron content is 0.35%, and the N content of the high molecular weight polyisobutylene succinimide is 1.1%.

4. The stationary gas engine oil compound according to claim 3, characterized in that: The high molecular weight polyisobutylene succinimide is prepared by firstly reacting high molecular weight polyisobutylene with maleic anhydride to obtain polyisobutylene maleic anhydride, and then using the polyisobutylene maleic anhydride as a raw material to react with polyamine in different preset proportions.

5. The stationary gas engine oil compound according to claim 1, characterized in that: The alkyl salicylate is high-base calcium salicylate, and the structural formula of the high-base calcium salicylate is: Among them, R1 and R2 are C14-C18, C20-C24, and C24-C28 alkyl groups respectively.

6. The stationary gas engine oil package according to claim 1, characterized in that: The structural formula of the phenolic ester antioxidant is: Wherein, R is a straight chain or branched chain alkyl group having 1 to 12 carbon atoms.

7. The stationary gas engine oil package according to claim 1, characterized in that: The structural formula of the nitrogen-containing hindered phenol is: Wherein, R3 and R4 represent a straight chain or branched chain alkyl group having 1 to 12 carbon atoms respectively.

8. The stationary gas engine oil package according to claim 7, characterized in that: The nitrogen-containing hindered phenol adopts diisooctylamine-hindered phenol, and the structural formula is:

9. A method for preparing a stationary gas engine oil compound, characterized in that: For preparing a stationary gas engine oil compound according to any one of claims 1 to 8, comprising: Adding polyisobutylene succinimide, alkyl salicylate, phenol ester antioxidant and nitrogen-containing hindered phenol into a container in sequence; The components in the container are heated to 55-65° C. while stirring, and stirred at 600 rpm for 1 hour; Add dioctyl alkyl zinc thiophosphate and base oil at 60-65° C., continue stirring for 2 hours, and filter to obtain the stationary gas engine oil composite.

10. A stationary gas engine oil, characterized in that: The base oil and the stationary gas engine oil composite according to any one of claims 1 to 8 are prepared according to a preset ratio.

Images