Lubricating oil composite additive and marine cylinder oil composition containing same

Abstract

The invention relates to a lubricating oil composite additive and a marine cylinder oil composition containing the lubricating oil composite additive. The lubricating oil composite additive is prepared from the following components in percentage by weight: 30 to 85 percent of sulfonate, 5 to 30 percent of sulfurized alkylphenate, 0.5 to 30 percent of ashless dispersant and 0.1 to 20 percent of antioxidant, wherein the 100 DEG C kinematic viscosity of the ashless dispersant is greater than or equal to 400mm < 2 > / s; the sulfonate is a combination of sulfonate with at least one base number; the total base number of the sulfurized alkyl phenate is greater than or equal to 150 mgKOH / g. By optimizing the proportion of the sulfonate, the sulfurized alkylphenate and the high-molecular-weight ashless dispersant and adding the antioxidant, the low-base-number lubricating oil composite additive of low-sulfur fuel oil, which has good comprehensive properties such as high detergency, high dispersity and high oxidation resistance, is obtained and has the advantages of high viscosity, high viscosity, high viscosity, high viscosity, high viscosity, low cost and the like. The bright stock can provide good detergency, dispersibility and oxidation stability, can efficiently control sediments, and can realize low addition amount of bright stock.

Description

Technical Field

[0001] This invention relates to the field of lubricating oil technology, and more particularly to a low-alkalinity marine cylinder oil composition that meets the requirements of low-sulfur fuel oil, as well as a lubricating oil composite additive. Background Technology

[0002] The International Maritime Organization (IMO)-led International Convention for the Prevention of Pollution from Ships (MARPOL) stipulates that, effective January 1, 2020, the sulfur content of marine fuel oil must not exceed 0.5%, and within Emission Control Areas (ECAs), it must not exceed 0.1%. This has directly promoted the use of low-sulfur fuel oil. Low-sulfur fuel oil typically has a lower acid value, less corrosiveness, and produces fewer acidic substances during combustion. Therefore, the demand for high-alkalinity cylinder oil is reduced, requiring a lower base value. International OEMs recommend that ships using fuel with a sulfur content below 0.5% prioritize the use of cylinder oil with a base value between 30-50 mg KOH / g. However, the use of low-sulfur fuel oil presents several challenges, including increased acidity due to a higher acid value, decreased lubricity due to lower sulfur content, easier formation of asphalt deposits, and accelerated engine wear due to the introduction of catalyst powder during low-sulfur fuel production. In severe cases, this can lead to various problems such as cylinder scoring, high-pressure pump seizure, and exhaust valve damage.

[0003] Furthermore, on July 8, 2021, dodecylphenol (TPP) was added to the EU's SVHC list. Substances listed as SVHCs require disclosure when added at a concentration of ≥0.1%. This means that mixtures containing more than 0.1% TPP will also exhibit TPP hazards and be subject to TPP regulatory requirements. Marine cylinder oils typically use sulfurized alkylphenol salts to meet detergency and antioxidant requirements. However, commercially available sulfurized alkylphenol salts generally have high TPP content, failing to meet the requirement of <0.1% TPP content in marine cylinder oils. Therefore, compliance with TPP regulations is necessary.

[0004] The above problems are usually solved by single-agent additives, formulation optimization, and selection of high-performance base oils, with additive formulation optimization playing a crucial role. Regarding base oil selection, conventional marine cylinder oil compounds contain a large amount of high-viscosity bright oil in marine lubricants. The presence of aromatic compounds with oxidative stability affects the performance of the lubricant. Furthermore, the supply of bright oil is decreasing, necessitating alternative solutions to achieve the required viscosity when using large quantities of bright oil. Therefore, there is an urgent need to develop a low-alkalinity marine cylinder oil additive and corresponding marine cylinder oil composition that meets the requirements of low-sulfur fuel oil usage, while also satisfying high cleanliness, high dispersibility, and high antioxidant properties, thereby expanding the application areas and scope of low-alkalinity marine cylinder oils for low-sulfur fuel oils. Summary of the Invention

[0005] This invention provides a lubricating oil composite additive comprising the following components based on the total weight of the composite additive: 30-85wt% sulfonates, 5-30 wt% sulfide alkylphenol salts, 0.5-30 wt% ashless dispersant, and 0.1-20 wt% antioxidants; Among them, the kinematic viscosity at 100℃ without ash dispersant is ≥400 mmHg. 2 / s; The total base value of the sulfide alkylphenol salt is ≥150 mgKOH / g.

[0006] In some embodiments, the sulfonate is a combination of at least two sulfonates with different base values, preferably a combination of a high base value sulfonate and a low base value sulfonate, more preferably, the weight ratio of the high base value sulfonate to the low base value sulfonate is 0.5:1 to 5:1, preferably 1:1 to 4:1, and more preferably 1.2:1 to 3:1.

[0007] In some embodiments, the dodecylphenol content in the sulfurized alkylphenol salt is <0.5%, based on the total weight of the sulfurized alkylphenol salt; and / or The sulfide alkylphenol salt is calcium sulfide alkylphenol with an alkalinity ≥ 150 mgKOH / g.

[0008] In some embodiments, the ashless dispersant is a polyisobutylene succinimide dispersant, preferably selected from one or more of high molecular weight polyisobutylene succinimide dispersants, polyisobutylene succinimide dispersants, bispolyisobutylene succinimide dispersants, and monopolyisobutylene succinimide dispersants; more preferably, the ashless dispersant is selected from one or more of high molecular weight polyisobutylene succinimide dispersants, polyisobutylene succinimide dispersants, and bispolyisobutylene succinimide dispersants.

[0009] In some embodiments, the molecular weight of the polyisobutylene succinimide dispersant is 400-10000 Da, for example, the molecular weight can be 500 Da, 800 Da, 950 Da, 1000 Da, 1500 Da, 1800 Da, 2000 Da, 2500 Da, 2800 Da, 3500 Da, 4000 Da, 5000 Da, 6000 Da, 7000 Da, 8000 Da, 9000 Da, more preferably 800-3000 Da.

[0010] In some embodiments, the antioxidant is at least one of zinc dialkyl dithiophosphate, amine antioxidant, and hindered phenolic antioxidant. Preferably, the zinc dialkyl dithiophosphate is selected from one or more combinations of primary alkyl zinc salts, secondary alkyl zinc salts, and alkylaryl zinc salts; more preferably, it is one or more combinations of primary alkyl zinc salts and secondary alkyl zinc salts. The amine antioxidant is selected from secondary amine antioxidants, hindered p-phenylenediamine antioxidants, naphthylamine antioxidants, and ketamine / aldehyde amine antioxidants, preferably one or more combinations of secondary amine antioxidants, hindered p-phenylenediamine antioxidants, and naphthylamine antioxidants, more preferably one or more combinations of secondary amine antioxidants and hindered p-phenylenediamine antioxidants; The hindered phenolic antioxidant is selected from one or more combinations of monophenol hindered phenolic antioxidants, bisphenol hindered phenolic antioxidants, and polyphenol hindered phenolic antioxidants.

[0011] In some embodiments, the composite additive further comprises an auxiliary agent selected from one or more of antifoaming agents, friction modifiers, rust inhibitors, demulsifiers, and metal deactivators.

[0012] In some embodiments, the composite additive has a total base number ≥160 mgKOH / g, an S content ≥1.6%, an N content ≥0.30%, and a kinematic viscosity of 50-450 mmHg at 100°C. 2 / s.

[0013] This application also relates to a marine cylinder oil composition comprising the following components by weight of the total marine cylinder oil composition: 5-35 wt% of the above-mentioned lubricating oil compound additives of this application; and 65-95wt% base oil.

[0014] This application also relates to a marine cylinder oil composition comprising the following components by weight of the total marine cylinder oil composition: 5-15 wt% sulfonates, 0.5-7wt% sulfide alkylphenol salts, 0.5-10wt% ashless dispersant, 0.01-2wt% antioxidant, 0-0.7% of adjuvants, and 65-95% base oil; Among them, the kinematic viscosity at 100℃ without ash dispersant is ≥400 mmHg. 2 / s; The total base value of the sulfide alkylphenol salt is ≥150 mgKOH / g.

[0015] This application's composite additive optimizes the ratio of sulfonates, sulfurized alkylphenol salts, and high molecular weight ashless dispersants, and adds antioxidants to obtain a low-alkalinity lubricating oil composite additive for low-sulfur fuel oil with excellent comprehensive performance, including high cleaning power, high dispersibility, and high antioxidant properties. It has high viscosity, provides good cleaning power, dispersibility, and oxidation stability, can efficiently control deposits, and can achieve low addition of bright oil. Attached Figure Description

[0016] Figure 1 This is a photograph of the sediments taken after the coking plate experiment of oil product 1; Figure 2 This is a photograph of the sediments taken after the coking plate experiment of oil product 2; Figure 3 This is a photograph of the sediments taken after the coking plate experiment of control oil 1; Figure 4 Photographs of oil spots taken for the spot dispersion experiment (dispersibility test) of oil sample 1; Figure 5 Photographs of the heat pipe taken after the Komatsu heat pipe experiment (KHT@330℃ JPI-5S-55-99) for oil product 1. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way.

[0018] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments.

[0019] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0020] In a first aspect, this application relates to a lubricating oil compound additive comprising the following components by weight of the total compound additive: 30-85wt% sulfonates, 5-30 wt% sulfide alkylphenol salts, 0.5-30 wt% ashless dispersant, and 0.1-20 wt% antioxidants; Among them, the kinematic viscosity at 100℃ without ash dispersant is ≥400 mmHg. 2 / s; The alkylphenol salt is calcium alkylphenol sulfide with an alkalinity ≥ 150 mgKOH / g.

[0021] The components of the composite additive of this application are described below.

[0022] The compound additive of this application contains a sulfonate. This sulfonate, together with a sulfurized alkylphenol salt, can act as a detergent.

[0023] In some embodiments, the sulfonate is a combination of at least two sulfonates with different base values, preferably a combination of a high-base-value sulfonate and a low-base-value sulfonate, wherein the weight ratio of the high-base-value sulfonate to the low-base-value sulfonate is from 0.5:1 to 5:1, for example, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 and any value between these, preferably 1:1 to 4:1, more preferably 1.2:1 to 3:1. The inventors of this application have discovered that using this combination of high-base-value sulfonates and low-base-value sulfonates, the resulting composite additive exhibits good acid neutralization ability, detergent effect, dispersion effect, solubilization effect, and rust-preventing effect. The sulfonate can be calcium sulfonate, magnesium sulfonate, sodium sulfonate, barium sulfonate, or lithium sulfonate. The ultra-high base value sulfonate is preferably ultra-high base value calcium sulfonate, and the low base value sulfonate is preferably low base value calcium sulfonate. The source of the raw materials is not specifically limited, including synthetic calcium sulfonates and petroleum calcium sulfonates. In this application, for sulfonates, "ultra-high base value" means a base value exceeding 350 mgKOH / g; "high base value" means a base value between 250 and 350 mgKOH / g; "medium base value" means a base value between 100 and 250 mgKOH / g; and "low base value" means a base value ≤ 35 mgKOH / g.

[0024] The composite additive of this application comprises a sulfurized alkylphenol salt. The sulfurized alkylphenol salt may be selected from calcium sulfurized alkylphenol, more preferably, at least one of ultra-high alkalinity calcium sulfurized alkylphenol, high alkalinity calcium sulfurized alkylphenol, medium alkalinity calcium sulfurized alkylphenol, and low alkalinity calcium sulfurized alkylphenol. In this application, for sulfurized alkylphenol salts, "ultra-high alkalinity" means an alkalinity greater than or equal to 300 mgKOH / g; "high alkalinity" means an alkalinity between 200 and 300 mgKOH / g; "medium alkalinity" means an alkalinity between 100 and 200 mgKOH / g; and "low alkalinity" means an alkalinity less than 100 mgKOH / g.

[0025] The total base value of the alkylphenol salt used in the composite additive of this application is ≥150 mgKOH / g. In some embodiments, the alkylphenol salt used in the composite additive of this application can be a combination of different types of alkylphenol salts, as long as the final total base value is ≥150 mgKOH / g. In some embodiments, the alkylphenol salt used in the composite additive of this application is an alkylphenol salt with a base value ≥150 mgKOH / g (especially calcium alkylphenol), and does not contain low-base-value alkylphenol salts. Using such high-base-value alkylphenol salts, the obtained composite additive has good acid neutralization ability, detergency, excellent antioxidant and anti-corrosion properties, and good anti-wear effect.

[0026] In some embodiments, the dodecylphenol content in the sulfurized alkylphenol salt is <0.5%, based on the total weight of the sulfurized alkylphenol salt. Using sulfurized alkylphenol salts with a free dodecylphenol content of <0.5% allows the composite additives of this application and the final marine cylinder oil to comply with the EU's SVHC list requirements.

[0027] Commonly used lubricating oil compound additives typically include alkyl salicylates. However, the inventors of this application have discovered that when alkyl salicylates are used in the compound additive system of this application, precipitation easily occurs after the alkyl salicylates and sulfonates are combined, and the storage viscosity changes significantly. Therefore, the lubricating oil compound additive of this application does not contain alkyl salicylates.

[0028] In some embodiments, the lubricating oil compound additive of this application does not contain naphthenate detergents.

[0029] The composite additive of this application includes an ashless dispersant, whose main functions are dispersion and solubilization. In some embodiments, the ashless dispersant is a polyisobutylene succinimide dispersant, preferably selected from one or more of high molecular weight polyisobutylene succinimide dispersants, bis and polyisobutylene succinimide dispersants, and monoisobutylene succinimide dispersants; more preferably, the ashless dispersant is selected from one or more of high molecular weight polyisobutylene succinimide dispersants and bis or polyisobutylene succinimide dispersants. Typically, high molecular weight polyisobutylene succinimide dispersants are synthesized from polyisobutylene with a molecular weight of about 2000 and maleic anhydride; bis and polyisobutylene succinimide dispersants are synthesized from polyisobutylene with a molecular weight of about 1000 and maleic anhydride; and monoisobutylene succinimide dispersants are synthesized from polyisobutylene with a molecular weight of about 1300 and maleic anhydride. Monoisobutylene succinimide, bis- and polyisobutylene succinimide have only one maleic anhydride attached to each polyisobutylene chain (PIB), while high molecular weight polyisobutylene succinimide has approximately two maleic anhydrides attached to one PIB. In this application, the kinematic viscosity at 100°C without ash dispersant is ≥400 mm⁻¹. 2 The molecular weight of the polyisobutylene used in its synthesis is in the range of 800-2500, and its structure is preferably selected from one or more of high molecular weight polyisobutylene succinimide dispersants, polyisobutylene succinimide dispersants, bispolyisobutylene succinimide dispersants, and monopolyisobutylene succinimide dispersants. Using such ashless dispersants, the resulting composite additive exhibits excellent thermal stability, good high-temperature detergency, low-temperature sludge dispersibility, soot dispersibility, and good oil solubility.

[0030] In some embodiments, based on the total weight of the composite additives, the amount of sulfonate is 30-85 wt% (e.g., 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, and any value between them, preferably 30 wt% to 60 wt%, or 35 wt% to 50 wt%, or 35 wt% to 45 wt%); the amount of sulfide alkylphenol salt is 5-30 wt% (e.g., 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30%; preferably 10 wt% to 25 wt%, or 12 wt% to 22 wt%); and the amount of ashless dispersant is 0.5-30 wt% (e.g., 1 wt%, 2 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 28 wt%, 30 wt%; preferably 4-30 wt%). (wt%, 5-20 wt%, or 6-15 wt%). Using this combination of sulfonates, alkylphenol salts, and ashless dispersants, the resulting composite additive exhibits excellent detergency (including acid neutralization, washing, and solubilizing effects), good antioxidant and anti-corrosion properties, good anti-wear properties, good rust prevention properties, and excellent dispersing properties.

[0031] The composite additive of this application contains 0.1-20 wt% of an antioxidant, such as 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 7 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, or 18 wt%, preferably 0.5-12 wt% or 1-10 wt%. In some embodiments, the antioxidant is at least one of dialkyl dithiophosphate zinc salt, amine antioxidant, or hindered phenolic antioxidant. Preferably, the dialkyl dithiophosphate zinc salt is selected from one or more combinations of primary alkyl zinc salt, secondary alkyl zinc salt, and alkylaryl zinc salt; more preferably, it is one or more combinations of primary alkyl zinc salt and secondary alkyl zinc salt, for example, it may be selected from T202, T203, T204, T205, and combinations thereof. The amine antioxidant is selected from secondary amine antioxidants, hindered p-phenylenediamine antioxidants, naphthylamine antioxidants, and ketamine / aldehyde amine antioxidants. Preferably, it is one or more combinations of secondary amine antioxidants, hindered p-phenylenediamine antioxidants, and naphthylamine antioxidants. More preferably, it is one or more combinations of secondary amine antioxidants and hindered p-phenylenediamine antioxidants. For example, it can be selected from antioxidant 5057, N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N,N'-di-secondary amine antioxidants. Butyl-p-phenylenediamine (antioxidant 4720), N-isopropyl-N'-phenyl-p-phenylenediamine (antioxidant 4010NA), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (antioxidant 4020), N-cyclohexyl-N'-phenyl-p-phenylenediamine (antioxidant 4010), N,N'-diphenyl-p-phenylenediamine (antioxidant PPD), N,N'-di(2-naphthyl)-p-phenylenediamine (antioxidant DNP), and combinations thereof. The hindered phenolic antioxidant is selected from one or more combinations of monophenol hindered phenolic antioxidants, bisphenol hindered phenolic antioxidants, and polyphenol hindered phenolic antioxidants. Examples of monophenol hindered phenolic antioxidants include 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol, and β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076). Examples of bisphenol hindered phenolic antioxidants include 2,2'-methylenebis(4-methyl- Antioxidant 2246 includes 6-tert-butylphenol and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (antioxidant 425); the hindered phenolic antioxidants include, for example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (antioxidant 1330) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010). Using these antioxidants can solve the problem of insufficient high-temperature oxidation stability of low-alkalinity marine cylinder oils, enabling efficient lubrication of low-sulfur fuel oil engines.

[0032] The composite additive may further include auxiliary agents selected from one or more of antifoaming agents, friction modifiers, rust inhibitors, demulsifiers, and metal deactivators. Various auxiliary agents commonly used in the art can be used, and will not be elaborated here. The amount of the auxiliary agent is 0.01-1 wt%, based on the total weight of the composite additive.

[0033] In some embodiments, the total base value of the composite additive of this application is ≥160 mgKOH / g, the S content is ≥1.6wt% (based on the total weight of the composite additive), and the N content is ≥0.30wt% (based on the total weight of the composite additive).

[0034] In some embodiments, the kinematic viscosity of the composite additive of this application at 100°C is 50-450 mm. 2 / s, for example, 50mm 2 / s, 100 mm 2 / s, 150mm 2 / s, 200 mm 2 / s, 250mm 2 / s, 300 mm 2 / s, 350mm 2 / s, 400 mm 2 / s, 450mm 2 / s and any values ​​in between.

[0035] The composite additive of this application can be prepared as follows: the above sulfonate, sulfide alkylphenol salt, ashless dispersant and antioxidant are added to a container, heated to 70-90℃ by mechanical stirring and mixed evenly and kept at the temperature for 30 minutes, and then cooled to room temperature to obtain the lubricating oil composite additive.

[0036] This application's composite additive optimizes the ratio of sulfonates, sulfurized alkylphenol salts, and high-molecular-weight ashless dispersants, and adds antioxidants to obtain a low-alkalinity lubricating oil composite additive for low-sulfur fuel oils with excellent comprehensive performance, including high detergency, high dispersibility, and high antioxidant properties. This composite additive can be formulated with base oils to create low-sulfur, low-alkalinity marine cylinder oils, and can reduce the amount of bright oil used in base oils by approximately 50%, reducing the cost of finished oils and increasing market competitiveness. Furthermore, this composite additive has high viscosity, providing excellent detergency, dispersibility, and oxidation stability, effectively controlling deposits, and meeting EU regulations on TPP and low bright oil addition. The application areas of this composite additive include, but are not limited to, cylinder oils, marine system oils, and marine medium-speed cylindrical piston diesel engine oils. Secondly, this application relates to a marine cylinder oil composition comprising the following components by weight of the total weight of the marine cylinder oil composition: 5-35 wt% of the lubricating oil compound additive of the first aspect of this application; and 65-95 wt% base oil.

[0037] Thirdly, this application relates to a marine cylinder oil composition comprising the following components by weight of the total marine cylinder oil composition: 5-15 wt% sulfonates, 0.5-7wt% sulfide alkylphenol salts, 0.5-10wt% ashless dispersant, 0.01-2wt% antioxidant, 0-0.7% of adjuvants, and 65-95% base oil; Among them, the kinematic viscosity at 100℃ without ash dispersant is ≥400 mmHg. 2 / s; The total base value of sulfide alkylphenol salts is ≥150 mgKOH / g.

[0038] As described above, the marine cylinder oil compositions of the second and third aspects of this application can be formulated from the lubricating oil composite additive of the first aspect of this application and base oil; alternatively, they can be directly formulated by adding each component to the base oil. For example, the lubricating oil composite additive and base oil can be mixed evenly at 50-70°C to obtain a finished marine cylinder oil that meets the viscosity requirements of SAE40 and SAE50. Alternatively, the components can be directly added to the base oil for mixing to obtain the corresponding finished marine cylinder oil. Both of these embodiments are within the protection scope of this application.

[0039] In some embodiments, the base oil is selected from at least one of API Group I base oil and API Group II base oil; wherein the bright oil accounts for ≤15 wt% based on the total weight of the marine cylinder oil composition.

[0040] In some embodiments, the base oil is selected from bright oils and neutral oils; the neutral oil is selected from oils with a Saybolt viscosity of 133-834 mmHg at 40°C. 2 / s of one or more API Class I and / or API Class II, preferably with a viscosity range of 302-334 mm. 2 / s, 440-496mm 2 / s, and 510-579mm 2 / s; the bright oil is selected from a Saybolt general viscosity of 82-211 mm at 100℃. 2 / s of one or more of API Class I and / or API Class II, preferably with a viscosity range of 120-134 mm. 2 / s, 125-143mm 2 / s and 143-156mm 2 / s.

[0041] In some embodiments, the base oil is a combination of API Group I and / or API Group II bright oil and API Group I and / or API Group II neutral oil, wherein the proportion of API Group I bright oil is ≤15wt%, based on the total weight of the marine cylinder oil composition.

[0042] Preferably, the basicity of the marine cylinder oil composition is 30-50 mg KOH / g; Preferably, the marine cylinder oil composition achieves SAE40 and / or SAE50 viscosity characteristics.

[0043] In one specific embodiment, the neutral oil is selected from one or more of neutral oil 100SN, neutral oil 150SN, and neutral oil 500SN; the bright oil is selected from one or more of bright oil 90BS, bright oil 120BS, and bright oil 150BS; and the HVI Group II base oil is selected from one or more of base oil 100N, base oil 150N, base oil 500N, base oil 600N, Mobil EHC110, Mobil EHC50, and Group II 150BS.

[0044] The present application will be further described in detail below through embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0045] Example 1 A low-alkalinity lubricating oil compound additive 1 that meets the requirements of low-sulfur fuel oil consists of the following components in weight percentage: 36% synthetic calcium sulfonate with a base number of 400 or higher (ultra-high base number synthetic calcium sulfonate, base number 400BN, trade name KTC400, Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.). 15% synthetic calcium sulfonate with a base value below 35 (low base value synthetic calcium sulfonate, base value 30BN, trade name KTC030, purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.). 20% high-alkalinity alkylphenol calcium sulfate (TPP content <0.5%, trade name KTP250D, Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.) 24% high molecular weight, high viscosity, ashless dispersant (kinematic viscosity ≥400 mmHg at 100℃) 2 / s, molecular weight around 2000, trade name KT1963, Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. 5% antioxidant (it is an amine antioxidant, trade name RIANOX 5057, Tianjin Lianlong New Material Co., Ltd.).

[0046] The kinematic viscosity of this composite additive 1 at 100°C is approximately 200 mm. 2 / s, total alkali value is 212mgKOH / g, S content is 1.8%, and N content is 0.6%.

[0047] Example 2 Composite additive 2 was obtained according to Example 1. The difference from Example 1 is that the high-alkalinity alkylphenol calcium sulfide is selected from commercially available products with conventional TPP content (TPP content of about 10%, trade name KTP250, Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.).

[0048] Comparative Example 1 Comparative composite additive 1 was obtained according to Example 1, the difference being that the ashless dispersant used in Example 1 was a low molecular weight ashless dispersant with a kinematic viscosity of 100 mmHg at 100°C. 2 Approximately / s (trade name KT1051, molecular weight approximately 1000, purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.).

[0049] The kinematic viscosity of the compound at 100°C is approximately 70 mm. 2 / s, total alkali value is 213mgKOH / g, S content is 1.8%, and N content is 0.6%.

[0050] Example of Refined Oil Preparation The composite additives from Examples 1-2 and Comparative Example 1 were mixed with the base oil in a ratio of 19% (by mass) of composite additives and 81% (by mass) of base oil to obtain the finished marine cylinder oil. The base oil consisted of API Group I base oil 150BS (i.e., bright oil) and API Group II base oil 500N (i.e., neutral oil). By adjusting the ratio of the two, the finished oil met the SAE50 standard (base number 30-50 mg KOH / g).

[0051] For the comparative compound additive 1 of Comparative Example 1, 26% API Group I base oil 150BS and 55% API Group II base oil 500N (i.e., neutral oil) are required to produce the finished marine cylinder oil with an SAE50 base number of 30-50 mgKOH / g (control oil 1).

[0052] For the compound additive 1 of Example 1, a finished marine cylinder oil (oil product 1) with an SAE 50 base number of 30-50 mg KOH / g can be prepared using 12% API Group I base oil 150BS (i.e., bright oil) and 69% API Group II base oil 500N (i.e., neutral oil). The TPP content in oil product 1 is 0.019%, which is less than 0.1%. Compared with the comparative compound additive 1 of Comparative Example 1, the amount of bright oil 150BS is reduced by 54%.

[0053] For the composite additive 2 in Example 2, a finished marine cylinder oil (oil product 2) with an SAE50 base number of 30-50 mgKOH / g can be prepared by using 12% API Group I base oil 150BS (i.e., bright oil) and 69% API Group II base oil 500N (i.e., neutral oil). The TPP in oil product 2 is 0.38%, which is greater than 0.1%.

[0054] Test data The obtained finished oil products (oil product 1, oil product 2, and control oil product 1) were tested, and the results are shown in Table 1 below: Table 1

[0055] The test methods are as follows: The "coking plate" was tested according to FTM791-3462; "Ship oil aging" is tested according to IP48; “PDSC@210℃, O2” is tested according to ASTM D6186; The "four-ball" test is conducted in accordance with ASTM D4172. "Dispersion" is tested according to ASTM D7899.

[0056] Note: The less coking deposits, the better; the higher the dispersibility, the better; the higher the antioxidant capacity (PDSC@210℃, O2), the better; the lower the anti-wear capacity (DM), the better; the lower the coefficient of friction, the better; and the lower the viscosity change and acid value increase (ship oil aging IP48), the better.

[0057] Figure 4 Photographs of oil spots taken for the spot dispersion experiment (dispersibility test) of oil sample 1; Figure 5 The image shows a heat pipe photograph taken after the Komatsu heat pipe experiment (KHT@330℃-JPI-5S-55-99) of oil product 1, with a rating of 8.5 and a deposit weight of 0.5 mg. This indicates that oil product 1 has excellent dispersibility, detergency, and acid neutralization ability.

[0058] Examples 3-6 and Comparative Examples 2-8 The composite additives for each example and comparative example were obtained according to the components listed in Tables 2 and 3 below, where the units are weight percentages (wt%).

[0059] Table 2

[0060] Table 3

[0061] A1 is ultra-high alkalinity synthetic calcium sulfonate with an alkalinity of 400. Its trade name is KTC400 and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. A2 is a high-alkalinity synthetic calcium sulfonate with an alkalinity of 300. Its trade name is KTC300 and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. A3 is a medium-alkalinity synthetic calcium sulfonate with an alkalinity of 150. Its trade name is KTC150 and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. A4 is a low-base-value synthetic calcium sulfonate with a base value of 30. Its trade name is KTC030 and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. B1 is ultra-high base value alkylphenol calcium sulfate with a base value of 300 and a TPP content of <0.5%. Its trade name is KTP300D and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. B2 is a high-base-value alkylphenol calcium sulfate with a base value of 250 and a TPP content of <0.5%. Its trade name is KTP250D, and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. B3 is a medium-base-value alkylphenol calcium sulfate with a base value of 150 and a TPP content of <0.5%. Its trade name is KTP150D, and it was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. C1 is a high molecular weight, high viscosity polyisobutylene succinimide ashless dispersant with a kinematic viscosity ≥400 mmHg at 100℃. 2 / s, product name KT1963, purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.; C2 is a low molecular weight ashless dispersant with a kinematic viscosity of 100 mmHg at 100°C. 2 The product, with a speed of approximately / s, is named KT1054 and was purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd. D1 is an amine antioxidant, marketed as RIANOX 5057, purchased from Tianjin Lianlong New Materials Co., Ltd.

[0062] According to the compound additive dosage (mass %) listed in Tables 2 and 3, the base oil accounts for (1 - compound additive dosage) (mass %). The compound additives in Tables 2 and 3 are mixed with the base oil to obtain the finished marine cylinder oil. The base oil consists of API Group I base oil 150BS (i.e., bright oil) and API Group II base oil 500N. By adjusting the ratio of the two, the finished oil meets the SAE50 standard (base number 30-50mgKOH / g).

[0063] The resulting finished oil products were tested, and the results are shown in Tables 4 and 5 below. Oil product 3 was obtained using the compound additive of Example 3, and control oil product 2 was obtained using the compound additive of Comparative Example 2. The others were similar.

[0064] Table 4

[0065] Table 5

[0066] The results show that by optimizing the ratio of sulfonate, sulfurized alkylphenol salt and high molecular weight ashless dispersant, and adding antioxidants, a low-alkalinity lubricating oil composite additive with good comprehensive performance such as high cleanliness, high dispersibility and high antioxidant properties can be obtained for low-sulfur fuel oil.

[0067] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A lubricating oil compound additive comprising the following components based on the total weight of said compound additive: 30-85wt% sulfonates, 5-30 wt% sulfide alkylphenol salts, 0.5-30 wt% ashless dispersant, and 0.1-20 wt% antioxidants; in, 100°C kinematic viscosity of ashless dispersant ≥ 400 mm 2 / s; The total base value of the sulfide alkylphenol salt is ≥150 mgKOH / g.

2. The lubricating oil composite additive according to claim 1, wherein, The sulfonate is a combination of at least two different base sulfonates, preferably a combination of ultra-high base sulfonate and low base sulfonate, more preferably, the weight ratio of the ultra-high base sulfonate and the low base sulfonate is 0.5:1 to 5:1, preferably 1:1 to 4:1, and more preferably 1.2:1 to 3:

1.

3. The lubricating oil composite additive according to claim 1, wherein, The dodecylphenol content in the sulfurized alkylphenol salt is <0.5%, based on the total weight of the sulfurized alkylphenol salt; and / or The sulfide alkylphenol salt is calcium sulfide alkylphenol with an alkalinity ≥ 150 mgKOH / g.

4. The lubricating oil composite additive according to claim 1, wherein, The ashless dispersant is a polyisobutylene succinimide dispersant, preferably selected from one or more of high molecular weight polyisobutylene succinimide dispersants, polyisobutylene succinimide dispersants, bispolyisobutylene succinimide dispersants, and monopolyisobutylene succinimide dispersants. The molecular weight of the polyisobutylene succinimide dispersant is 400-10000 Da, more preferably 800-3000 Da.

5. The lubricating oil composite additive according to claim 1, wherein, The antioxidant is at least one of zinc dialkyl dithiophosphate, amine antioxidants, and hindered phenolic antioxidants. Preferably, the dialkyl dithiophosphate zinc salt is selected from one or more combinations of primary alkyl zinc salts, secondary alkyl zinc salts, mixed primary and secondary alkyl zinc salts, and alkylaryl zinc salts; The amine antioxidant is selected from secondary amine antioxidants, hindered p-phenylenediamine antioxidants, naphthylamine and ketamine / aldehyde amine antioxidants, preferably one or more combinations of secondary amine antioxidants, hindered p-phenylenediamine antioxidants and naphthylamine antioxidants; The hindered phenolic antioxidant is selected from one or more combinations of monophenol hindered phenolic antioxidants, bisphenol hindered phenolic antioxidants, and polyphenol hindered phenolic antioxidants.

6. The lubricating oil composite additive according to claim 1, wherein, The composite additive also includes an auxiliary agent selected from one or more of antifoaming agents, friction modifiers, rust inhibitors, demulsifiers, and metal deactivators.

7. The lubricating oil composite additive according to claim 1, wherein, The total base number of the complex additive is ≥ 160 mgKOH / g, the S content is ≥ 1.6%, the N content is ≥ 0.30%, and the kinematic viscosity at 100°C is 50-450 mm 2 / s.

8. A marine cylinder oil composition comprising the following components by weight of the total marine cylinder oil composition: 5-35 wt% of the lubricating oil compound additive according to any one of claims 1-7; and 65-95wt% base oil.

9. A marine cylinder oil composition comprising the following components by weight of the total weight of the marine cylinder oil composition: 5-15 wt% sulfonates, 0.5-7 wt% sulfide alkylphenol salts, 0.5-10wt% ashless dispersant, 0.01-2wt% antioxidant, 0-0.7% of adjuvants, and 65-95% base oil; in, 100°C kinematic viscosity of ashless dispersant ≥ 400 mm 2 / s; The total base value of the sulfide alkylphenol salt is ≥150 mgKOH / g.

10. The marine cylinder oil composition according to claim 8 or 9, wherein, The base oil is selected from at least one of API Group I and API Group II base oils; preferably, the base oil is selected from bright oil and neutral oil, wherein the proportion of bright oil is ≤15wt%, based on the total weight of the marine cylinder oil composition; the neutral oil is selected from oils with a Systèmes viscosity of 133-834 mmHg at 40°C. 2 The bright oil is selected from one or more API Class I and / or API Class II, and the bright oil is selected from those with a Saybolt general viscosity of 82-211 mm at 100°C. 2 / s contains one or more of API Class I and / or API Class II, Preferably, the basicity of the marine cylinder oil composition is 30-50 mg KOH / g; Preferably, the marine cylinder oil composition achieves SAE 40 and / or SAE 50 viscosity characteristics; Preferably, the base oil is a combination of API Group I bright oil and API Group II neutral oil; wherein the proportion of API Group I bright oil is ≤15wt%, based on the total weight of the marine cylinder oil composition.

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