An anti-wear hydraulic oil complex agent with high water separation performance and a preparation method thereof

Abstract

The present application relates to the field of hydraulic oil complex agent, and more particularly to an anti-wear hydraulic oil complex agent with high water separation performance and a preparation method thereof, the anti-wear hydraulic oil complex agent comprises the following components in parts by weight: zinc dialkyldithiophosphate 30-80 parts, phenolic ester type antioxidant 1-20 parts, alkyl diphenylamine antioxidant 1-10 parts, sulfided alkyl phenol calcium detergent 1-10 parts, dinonyl naphthalene sulfonate anti-rust agent 5-50 parts, azole metal deactivator 1-5 parts, base oil 0-20 parts. The hydraulic oil product prepared by the hydraulic oil complex agent provided by the present application has excellent water separation performance, and at the same time meets the performance requirements of anti-wear, anti-oxidation, anti-rust and the like.

Description

Technical Field

[0001] This invention relates to the field of hydraulic oil composites, and more particularly to an anti-wear hydraulic oil composite with high water separation performance and its preparation method. Background Technology

[0002] Water contamination of hydraulic oil during prolonged use, caused by factors such as seal failure and leakage, condensation, and contamination during oil changes, is a significant factor contributing to oil performance degradation and shortened lifespan. When hydraulic oil becomes contaminated with water, it easily forms an emulsion under the vigorous agitation of the pump. If the hydraulic oil cannot quickly separate from the water, a stable oil film cannot form between the contact surfaces of friction components, reducing the hydraulic oil's anti-wear properties, accelerating oil aging and additive degradation, producing deposits, and causing problems such as equipment corrosion, increased wear, and filter clogging. Therefore, hydraulic oils are required to have excellent water-separating properties, allowing water to settle to the bottom of the tank and preventing the formation of a stable emulsion. Currently, hydraulic oils with excellent water-separating properties are in high demand among industrial oil customers in fields such as construction machinery and coal mining.

[0003] Zinc dialkyl dithiophosphate, as a multifunctional additive with antioxidant, anti-wear, and anti-corrosion properties, is a mainstream product in the hydraulic oil market. Hydraulic oils formulated with zinc as the main component are low-cost and have excellent overall performance, meeting the needs of most hydraulic systems. Currently, long-chain primary alkyl thiophosphates used in hydraulic oils possess a certain degree of surface activity. Detergents, dispersants, rust inhibitors, and metal passivators used to ensure good overall performance of hydraulic oils are all surface-active substances. These substances adsorb onto the oil-water interface, forming a robust interfacial film that easily leads to poor oil demulsibility and difficulty in oil-water separation. Adding demulsifiers to hydraulic oils alters the type or interfacial properties of the emulsion, making it unstable and causing demulsification, thereby improving the water separation performance of the hydraulic oil. Selecting additives with good oil solubility can reduce the amount adsorbed at the oil-water interface, further enhancing the water separation performance. However, additives and base oils in hydraulic oils deteriorate upon oxidation, producing surface-active oxides that easily form W / O emulsions, worsening the oil's demulsibility. Improving the water separation performance of hydraulic oils during use also requires good oxidation stability and storage stability. The development of hydraulic oil composites with excellent demulsibility requires careful selection and balancing of the types and dosages of various additives, ensuring that the oil's anti-wear, rust prevention, and thermal stability meet standard requirements. Currently, there is an urgent need to provide an anti-wear hydraulic oil composite with outstanding water separation performance. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an anti-wear hydraulic oil composite agent with high water separation performance and its preparation method.

[0005] In a first aspect, the anti-wear hydraulic oil compound provided by the present invention comprises the following components in parts by weight: 30-80 parts of zinc dialkyl dithiophosphate, 1-20 parts of phenolic ester antioxidant, 1-10 parts of alkyl diphenylamine antioxidant, 1-10 parts of sulfide alkylphenol calcium detergent, 5-50 parts of dinonylnaphthalene sulfonate rust inhibitor, 1-5 parts of azole metal deactivator, and 0-20 parts of base oil.

[0006] The anti-wear hydraulic oil compound provided by this invention, formulated with zinc dialkyl dithiophosphate, phenolic ester antioxidants, alkyl diphenylamine antioxidants, sulfurized alkylphenol calcium detergents, dinonylnaphthalene sulfonate rust inhibitors, azole metal deactivators, etc., has the proposed water separation performance. The high-pressure anti-wear hydraulic oil formulated with this anti-wear hydraulic oil compound, base oil, pour point depressant, viscosity index agent, and antifoaming agent can better meet the requirements of national standard GB 11118.1 while having excellent comprehensive performance, especially outstanding water separation performance.

[0007] Preferably, the dialkyl dithiophosphate zinc is a long-chain primary alkyl thiophosphate zinc, more preferably dioctyl dithiophosphate zinc T203. In this invention, the dialkyl dithiophosphate zinc has multiple functions in hydraulic oil, including extreme pressure anti-wear, corrosion and rust prevention, and oxidation resistance.

[0008] Preferably, the phenolic ester antioxidant is selected from one or more of T512 (3,5-di-tert-butyl-4-hydroxyphenylpropionate), IRGANOX L135 (liquid high molecular weight phenolic ester antioxidant), and KT 5135 (liquid high molecular weight phenolic ester ashless antioxidant), preferably IRGANOX L135 or KT 5135.

[0009] Further preferably, the alkyl diphenylamine antioxidant is selected from one or more of bis(octyl)diphenylamine, butyl(octyl)diphenylamine, and dinonyldiphenylamine, preferably dinonyldiphenylamine.

[0010] In this invention, by using specific phenolic ester antioxidants and alkyl diphenylamine antioxidants together as a composite antioxidant, a synergistic effect on antioxidant performance is achieved.

[0011] Preferably, the alkylphenol calcium sulfurized detergent is medium-alkalinity alkylphenol calcium sulfurized T115A or high-alkalinity alkylphenol calcium sulfurized T115B. In this invention, alkylphenol calcium sulfurized exhibits excellent oxidation inhibition properties, effectively reducing the acid value of the aqueous layer in hydrolysis stability tests and improving the hydrolysis stability of oil products. The alkylphenol calcium sulfurized detergent also has excellent solubilizing and dispersing effects on oil sludge, thereby improving the thermal stability of the oil products.

[0012] Preferably, the dinonylnaphthalene sulfonate rust inhibitor is selected from one or more of neutral dinonylnaphthalene sulfonate, neutral dinonylnaphthalene sulfonate, and neutral dinonylnaphthalene sulfonate, with neutral dinonylnaphthalene sulfonate being the most preferred. In this invention, the use of a specific neutral dinonylnaphthalene sulfonate in conjunction with specific antioxidants and other components further improves the water separation performance of the anti-wear hydraulic oil.

[0013] Preferably, the azole metal deactivator is one or a mixture of benzotriazole derivative T552 (provided by Changsha Wangcheng Petrochemical Co., Ltd.), toluene-triazole derivative Irgamet 39, and thiadiazole derivative T561. In this invention, the above-mentioned azole metal deactivators, acting as metal passivators, achieve the effect of protecting metals, especially copper, to varying degrees through multiple functions such as replenishing active sulfur, forming chelates with metal ions, or forming a protective film on the metal surface. Because the metal passivator forms a protective film with the metal, it improves the catalytic oxidation of oil by the metal, and therefore also exhibits good antioxidant properties.

[0014] Further preferably, the base oil is an API Group II base oil, preferably with a viscosity index of 80-120, a sulfur content ≤0.03%, and a saturated hydrocarbon content >90%. In this invention, the base oil (Group II oil) used meets the technical requirements of API Group II oils (using hydrocracking or hydroisomerization cracking processes), with a viscosity index of 80-120, a sulfur content ≤0.03%, and a saturated hydrocarbon content >90%; such as II6 and II4 base oils produced by Shanghai Gaoqiao.

[0015] Further preferred embodiment of the present invention: the anti-wear hydraulic oil composite agent comprises the following components in parts by weight:

[0016]

[0017]

[0018] More preferably, the anti-wear hydraulic oil compound comprises the following components in parts by weight:

[0019]

[0020] In this invention, experimental research has shown that when 2-8 parts of phenolic ester antioxidant (IRGANOX L135 or KT5135) and 1-4 parts of alkyl diphenylamine antioxidant (dinonyl diphenylamine) are used in combination, by adjusting the amount of dinonyl naphthalene sulfonate rust inhibitor to 15-30 parts, the antioxidant properties of the oil can be further improved, the hydrolytic stability and thermal stability can be improved, and the formulated anti-wear hydraulic oil can exhibit better water separation performance.

[0021] The anti-wear hydraulic oil composite agent with high water separation performance provided by the present invention, under the condition of 54°C test temperature and oil-water volume ratio of 1:1, the emulsion takes 3 to 6 minutes to reach 3 mL, and under the condition of oil-water volume ratio of 7:1, the volume ratio of water separated is 80% to 90% in 30 minutes.

[0022] According to the present invention, the anti-wear hydraulic oil composite agent is blended with base oil, pour point depressant, viscosity index depressant, and antifoaming agent to obtain high-pressure anti-wear hydraulic oil; the base oil, pour point depressant, viscosity index depressant, and antifoaming agent can be conventional types in the art. In a preferred embodiment of the present invention, the anti-wear hydraulic oil composite agent is used to blend anti-wear hydraulic oil, preferably L-HM46 anti-wear hydraulic oil. In a preferred embodiment of the present invention, by weight percentage, the anti-wear hydraulic oil composite agent is 0.8%, Sinopec II6 base oil is 53%, Sinopec II10 base oil is 46%, polymethyl methacrylate pour point depressant is 0.2%, and composite antifoaming agent is 50 ppm.

[0023] Secondly, the present invention also provides a method for preparing the anti-wear hydraulic oil composite composition, comprising: mixing zinc dialkyl dithiophosphate, phenolic ester antioxidant, alkyl diphenylamine antioxidant, calcium sulfide phenol detergent, dinonylnaphthalene sulfonate rust inhibitor, azole metal deactivator, and base oil, heating to 50-90°C, stirring for 60-300 min, and filtering.

[0024] The beneficial effects of this invention are at least as follows: By selecting long-chain primary alkyl thiophosphate zinc with good oil solubility and weak surface activity, phenolic ester antioxidants, alkyl diphenylamine antioxidants, sulfurized alkylphenol calcium detergents, and azole metal deactivators, and compounding them with dinonylnaphthalene sulfonate rust inhibitors with demulsifying properties, the interaction of each component makes the hydraulic oil formulated using this invention have more outstanding water separation performance, while meeting the requirements for anti-wear, anti-oxidation, and rust prevention. The hydraulic oil compound of this invention does not contain high molecular weight polyether demulsifiers, avoiding problems such as oil turbidity and precipitation caused by the addition of a large amount of demulsifiers. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise specified, all techniques or conditions used in the following examples are conventional methods or performed in accordance with techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents and instruments used, unless otherwise specified, are all conventional products that can be purchased from legitimate channels.

[0027] Unless otherwise stated, all materials, reagents, etc. used in the following examples are commercially available.

[0028] In this embodiment of the invention, the dioctyl dithiophosphate zinc used was dioctyl dithiophosphate zinc T203 purchased from Wuxi Southern Petroleum Additives Co., Ltd.; the IRGANOX L135 used was a liquid high molecular weight phenolic antioxidant purchased from BASF; the dinonyl diphenylamine used was KT5535 purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.; the sulfide alkylphenol calcium used was dioctyl dithiophosphate zinc T121 purchased from Wuxi Southern Petroleum Additives Co., Ltd.; the KT5135 used was a phenolic ester type ashless antioxidant purchased from Jinzhou Kangtai Lubricating Oil Additives Co., Ltd.; the dinonyl naphthalene sulfonate used was a sample provided by Anhui Chengtai Chemical Co., Ltd.; the toluene-triazole derivative Irgamet 39 used was purchased from BASF; and the other azole metal deactivators used were samples provided by Changsha Wangcheng.

[0029] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the invention.

[0030] Example 1

[0031] This embodiment provides an anti-wear hydraulic oil composite agent with high water separation performance, which is composed of the following components:

[0032] 60% zinc dioctyl dithiophosphate, 8% IRGANOX L135, 4% dinonyl diphenylamine, 6% calcium alkylphenol sulfide, 15% zinc dinonyl naphthalene sulfonate, 1% benzotriazole derivative T552, 1% thiadiazole derivative T561, and 5% II6 base oil.

[0033] This embodiment also provides a method for preparing the anti-wear hydraulic oil composite with high water separation performance: Zinc dialkyl dithiophosphate, phenolic ester antioxidant, alkyl diphenylamine antioxidant, calcium sulfide phenol detergent, dinonylnaphthalene sulfonate rust inhibitor, azole metal deactivator and base oil are mixed according to the components and their dosage in the formula, heated to 60-70°C, stirred for 120 min, and filtered.

[0034] Example 2

[0035] This embodiment provides an anti-wear hydraulic oil composite agent with excellent water-repellent properties, which is composed of the following components:

[0036] 50% zinc dioctyl dithiophosphate, 9% IRGANOX L135, 3% dinonyl diphenylamine, 8% calcium alkylphenol sulfide, 23% zinc dinonyl naphthalene sulfonate, 2% thiadiazole derivative T561, and 5% II6 base oil.

[0037] The preparation method of the anti-wear hydraulic oil composite agent with high water separation performance provided in this embodiment is the same as that in Embodiment 1.

[0038] Example 3

[0039] This embodiment provides an anti-wear hydraulic oil composite agent with high water separation performance, which is composed of the following components:

[0040] Dioctyl dithiophosphate zinc 55%, KT5135 15%, dinonyl diphenylamine 7%, alkylphenol calcium sulfide 8%, dinonyl naphthalene sulfonate calcium 12%, thiadiazole derivative T561 1%, II6 base oil 2%.

[0041] The preparation method of the anti-wear hydraulic oil composite agent with high water separation performance provided in this embodiment is the same as that in Embodiment 1.

[0042] Example 4

[0043] This embodiment provides an anti-wear hydraulic oil composite agent with high water separation performance, which is composed of the following components:

[0044] Dioctyl dithiophosphate zinc 65%, IRGANOX L135 8%, dinonyl diphenylamine 2%, alkylphenol calcium sulfide 8%, dinonyl naphthalene sulfonate calcium 10%, toluene triazole derivative Irgamet 39 1.0%, thiadiazole derivative T561 0.5%, II6 base oil 5.5%.

[0045] Comparative Example 1

[0046] This comparative example provides an anti-wear hydraulic oil compound, composed of the following components:

[0047] Dioctyl dithiophosphate zinc 60%, 2,6-di-tert-butyl-p-cresol 8%, dinonyl diphenylamine 4%, high-base-value synthetic calcium sulfonate T106 6%, dinonylnaphthalene sulfonate zinc 15%, benzotriazole derivative T552 1%, thiadiazole derivative T561 1%, II6 base oil 5%.

[0048] The preparation method of the anti-wear hydraulic oil composite agent provided in this comparative example is the same as that in Example 1.

[0049] Comparative Example 2

[0050] This comparative example provides an anti-wear hydraulic oil compound, composed of the following components:

[0051] Dioctyl dithiophosphate zinc 65%, IRGANOX L135 8%, dinonyl diphenylamine 2%, alkylphenol calcium sulfide 8%, alkenyl succinate half ester T747 10%, toluene triazole derivative Irgamet 39 1.0%, thiadiazole derivative T561 0.5%, II6 base oil 5.5%.

[0052] The preparation method of the anti-wear hydraulic oil composite agent provided in this comparative example is the same as that in Example 1.

[0053] Comparative Example 3

[0054] This comparative example provides the product of Example 1 of patent CN113831948A, which is composed of 40 parts of zinc dialkyl dithiophosphate, 20 parts of 2,6-di-tert-butylphenol, 10 parts of 2,6-di-tert-butyl-p-cresol, 5 parts of calcium dinonylnaphthalenesulfonate, 5 parts of high-base-value sulfurized alkylphenol calcium, 3 parts of methyltriazole derivative, and 17 parts of neutral base oil.

[0055] Comparative Example 4

[0056] This comparative example provides a hydraulic oil product compound from a foreign company, whose components include 45-55% zinc dioctyl dithiophosphate, 15-25% 2,6-di-tert-butylphenol, 3-5% dinonyl diphenylamine, and 0.5-1% calcium dinonyl naphthalene sulfonate, among other components.

[0057] Test case

[0058] The anti-wear hydraulic oil composite agent of the above-mentioned embodiments and comparative examples was used to formulate L-HM46 anti-wear hydraulic oil at a dosage of 0.8% by weight, and performance tests were carried out. The dosage of other components was as follows: 53% Sinopec II6 base oil, 46% Sinopec II10 base oil, 0.2% polymethyl methacrylate pour point depressant, and 50 ppm composite antifoaming agent.

[0059] Basic performance tests:

[0060] The L-HM46 anti-wear hydraulic oil formulated in the embodiments and comparative examples of the present invention was tested according to the main requirements and test methods of GB 11118.1-2011. The test results are shown in Table 1.

[0061] Table 1 Basic Performance Tests

[0062]

[0063]

[0064] The test results in Table 1 show that the anti-wear hydraulic oil formulated with the anti-wear hydraulic composite agent of the present invention meets the requirements of GB 11118.1-2011 and has better antioxidant and hydrolytic stability properties.

[0065] Comparative test of water separation performance:

[0066] The anti-wear hydraulic oils formulated with hydraulic oil composites in Examples 1-4 and Comparative Examples 1-4 of this invention were tested for their anti-emulsification properties using GB / T 7305. The GB / T 7305 standard test method involves placing 40 mL of test oil and 40 mL of distilled water in a graduated cylinder, stirring for 5 minutes at 54°C or 82°C, and recording the time required for the emulsion to reduce to less than 3 mL (test temperature: 54°C). To further evaluate the actual situation of a small amount of water mixed in the hydraulic oil, an oil-to-water volume ratio of 7:1 was used. 70 mL of oil and 10 mL of water were added to a graduated cylinder, and the volume of water separated after 30 minutes was recorded (test temperature: 54°C). A higher volume of separated water indicates better water separation performance under high oil-to-water ratio conditions. Under high oil-to-water ratio conditions, the stability of the formed water-in-oil emulsion is enhanced, the water droplet aggregation and settling speed is slower, and the difficulty of water separation increases. Specific results are shown in the table below:

[0067] Table 2 Demulsibility Test

[0068]

[0069]

[0070] The test results in Table 2 show that the anti-wear hydraulic composite agent of the present invention has a significant advantage in water separation performance. Under standard test conditions (oil-water volume ratio 1:1), the test results of Examples 1-4 are better than the national standard requirements, better than Comparative Examples 1-3, and comparable to Comparative Example 4. Under high oil-water ratio (oil-water volume ratio 7:1) test conditions, Examples 1-4 show a more significant advantage in water separation performance than Comparative Examples 1-4, with a water separation rate of no less than 80% after 30 minutes, while the water separation rate of Comparative Examples 1-4 is no higher than 50% after 30 minutes. Comparative Examples 2 and 3 remain in an oil-in-water emulsion state, making oil-water separation difficult.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anti-wear hydraulic oil complex agent having high water separation performance, characterized by comprising: The anti-wear hydraulic oil composite agent comprises the following components in parts by weight: zinc dialkyldithiophosphate 30-80 parts, phenolic ester type antioxidant 1-20 parts, alkyl diphenylamine antioxidant 1-10 parts, sulfated alkyl phenol calcium detergent 1-10 parts, dinonyl naphthalene sulfonate anti-rust agent 5-50 parts, azole metal deactivator 1-5 parts, base oil 1-20 parts; the zinc dialkyldithiophosphate is zinc dioctyldithiophosphate; the phenolic ester type antioxidant is selected from one or both of IRGANOXL135 and KT 5135; the alkyl diphenylamine antioxidant is selected from one or more of bisoctyl diphenylamine, butyl octyl diphenylamine and dinonyl diphenylamine; the sulfated alkyl phenol calcium detergent is medium basicity sulfated alkyl phenol calcium T115A or high basicity sulfated alkyl phenol calcium T115B; the dinonyl naphthalene sulfonate anti-rust agent is selected from one or more of neutral dinonyl naphthalene sulfonate barium, neutral dinonyl naphthalene sulfonate zinc, neutral dinonyl naphthalene sulfonate calcium; the azole metal deactivator is a mixture of one or more of benzotriazole derivative T552, toluene benzotriazole derivative Irgamet 39 and thiazole derivative T561; and the base oil is API II type base oil.

2. The anti-wear hydraulic oil complex agent having high water separation performance according to claim 1, characterized by, The dinonyl naphthalene sulfonate anti-rust agent is selected as neutral dinonyl naphthalene sulfonate zinc.

3. The anti-wear hydraulic oil complex agent having high water separation performance according to claim 1, characterized by, The anti-wear hydraulic oil composite agent comprises the following components in parts by weight:

4. The anti-wear hydraulic oil complex agent with high water separation performance according to claim 3, characterized by, The anti-wear hydraulic oil composite agent comprises the following components in parts by weight:

5. The method of producing the anti-wear hydraulic oil complex agent having high water separation performance according to any one of claims 1 to 4, characterized by, The anti-wear hydraulic oil composite agent comprises the following components in parts by weight: The zinc dialkyldithiophosphate, the phenolic ester type antioxidant, the alkyl diphenylamine antioxidant, the sulfated alkyl phenol calcium detergent, the dinonyl naphthalene sulfonate anti-rust agent, the azole metal deactivator and the base oil are mixed, heated to 50-90 DEG C, stirred for 60-300 min, and filtered.

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