Anti-wear hydraulic oil complexing agent with high water diversion performance and preparation method of anti-wear hydraulic oil complexing agent

Abstract

The invention relates to the field of hydraulic oil complexing agents, in particular to an anti-wear hydraulic oil complexing agent with high water diversion performance and a preparation method thereof.The anti-wear hydraulic oil complexing agent is prepared from, by weight, 30-80 parts of zinc dialkyl dithiophosphate, 1-20 parts of phenolic ester type antioxidant, 1-10 parts of alkyl diphenylamine antioxidant and 1-10 parts of sulfurized calcium alkyl phenolate detergent. 5 to 50 parts of dinonyl naphthalene sulfonate antirust agent, 1 to 5 parts of azole metal deactivator and 0 to 20 parts of base oil. A hydraulic oil product prepared by the hydraulic oil complexing agent provided by the invention has excellent water diversion performance, and simultaneously meets the performance requirements of wear resistance, oxidation resistance, rust prevention and the like.

Description

Technical Field

[0001] The invention relates to the field of hydraulic oil compounding agents, and in particular to an anti-wear hydraulic oil compounding agent with high water separation performance and a preparation method thereof. Background Art

[0002] The water contamination problem faced by hydraulic oil during long-term use due to seal failure leakage, condensation, pollution during oil change, etc. is an important factor causing oil performance decay and shortened life. After the hydraulic oil is contaminated with water, it is easy to form an emulsion under the violent stirring of the oil pump. If the hydraulic oil cannot quickly achieve oil-water separation, it will not be able to form a stable oil film between the contact surfaces of the friction elements, reducing the wear resistance of the hydraulic oil, accelerating oil aging and additive degradation, and producing sediments, causing equipment corrosion, increased wear, filter clogging and other problems. Therefore, hydraulic oil is required to have good water separation performance, so that water sinks to the bottom of the oil tank without forming a stable emulsion. At present, hydraulic oil with excellent water separation performance is widely demanded by industrial oil customers in the fields of engineering machinery, coal, etc.

[0003] Zinc dialkyl dithiophosphate is a multifunctional additive with anti-oxidation, anti-wear and anti-corrosion properties. Anti-wear hydraulic oil prepared with zinc dialkyl dithiophosphate as the main agent has low cost and excellent comprehensive performance, meeting the use requirements of most hydraulic systems, and is still the mainstream variety in the hydraulic oil market. The long-chain primary alkyl sulfur phosphate currently used in hydraulic oil has a certain surface activity. To ensure that the hydraulic oil has good comprehensive performance, detergent dispersants, rust inhibitors, metal passivators, etc. are all surfactants. These substances are adsorbed on the oil-water interface to form a solid interface film, which easily causes the oil's anti-emulsification properties to deteriorate and makes it difficult to separate oil and water. By adding demulsifiers to hydraulic oil to change the type or interfacial properties of the emulsion, the emulsion becomes unstable and demulsifies, thereby improving the water separation performance of the hydraulic oil. Selecting additives with good oil solubility can reduce the amount of adsorption added at the oil-water interface to improve the water separation performance of the hydraulic oil. The additives and base oil in the hydraulic oil will deteriorate after oxidation, producing surface-active oxides, which are easy to form W / O type emulsions, making the oil's anti-emulsification properties worse. Improving the water separation performance of the hydraulic oil during use also requires the oil to have good oxidation stability and storage stability. The development of hydraulic oil compounds with excellent anti-emulsification performance requires careful selection and balance of the types and dosages of multiple additives, and ensuring that the oil's anti-wear, anti-rust, thermal stability, etc. meet the standard requirements. At present, there is an urgent need to provide an anti-wear hydraulic oil compound with outstanding water separation performance. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an anti-wear hydraulic oil compound with high water separation performance and a preparation method thereof.

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

[0006] The anti-wear hydraulic oil composite provided by the present invention is prepared by using zinc dialkyl dithiophosphate, phenol ester antioxidant, alkyl diphenylamine antioxidant, sulfided alkyl phenol calcium detergent, dinonylnaphthalene sulfonate rust inhibitor, azole metal deactivator and the like, and has the proposed water separation performance. The high-pressure anti-wear hydraulic oil prepared by using the anti-wear hydraulic oil composite with composite base oil, pour point depressant, viscosity index agent and anti-foaming agent can better meet the requirements of national standard GB 11118.1 and has excellent comprehensive performance, especially has outstanding water separation performance.

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

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

[0009] More preferably, the alkyl diphenylamine antioxidant is selected from one or more of dioctyl diphenylamine, butyl octyl diphenylamine and dinonyl diphenylamine, preferably dinonyl diphenylamine.

[0010] In the present invention, a specific phenol ester antioxidant and an alkyl diphenylamine antioxidant are used together as a composite antioxidant, which has a synergistic effect on the antioxidant performance.

[0011] Preferably, the sulfurized alkyl phenate calcium detergent is medium base value sulfurized alkyl phenate calcium T115A or high base value sulfurized alkyl phenate calcium T115B. In the present invention, the sulfurized alkyl phenate calcium has excellent oxidation inhibition performance, can effectively reduce the acid value of the water layer in the hydrolysis stability test, improve the hydrolysis stability of the oil product, and the sulfurized alkyl phenate calcium detergent also has very good solubilization and dispersion effects on oil sludge, thereby improving the thermal stability of the oil product.

[0012] Preferably, the dinonylnaphthalenesulfonate rust inhibitor is selected from one or more of neutral dinonylnaphthalenesulfonate barium, neutral dinonylnaphthalenesulfonate zinc, and neutral dinonylnaphthalenesulfonate calcium, preferably neutral dinonylnaphthalenesulfonate zinc. In the present invention, the specific neutral dinonylnaphthalenesulfonate zinc is used together with the specific antioxidant and other components of the present invention to further improve the water separation performance of the anti-wear hydraulic oil.

[0013] Preferably, the azole metal deactivator is a mixture of one or more of benzotriazole derivative T552 (provided by Changsha Wangcheng Petrochemical Co., Ltd.), toluene triazole derivative Irgamet 39, and thiadiazole derivative T561. In the present invention, the azole metal deactivator as a metal passivator can achieve the effect of protecting metals, especially copper, to varying degrees through multiple effects such as collecting active sulfur, forming chelates with metal ions, or forming a protective film on the metal surface. Since the metal passivator forms a protective film with the metal, the catalytic oxidation of the metal to the oil is improved, so it also exhibits good antioxidant properties.

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

[0015] Further preferably, the preferred technical solution of the present invention is: the anti-wear hydraulic oil compound 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 the present invention, it is found through experimental research that when 2 to 8 parts of phenolic ester antioxidant (IRGANOX L135 or KT5135) and 1 to 4 parts of alkyl diphenylamine antioxidant (dinonyl diphenylamine) are used in combination, by adjusting the amount of dinonyl naphthalene sulfonate rust inhibitor to 15 to 30 parts, the antioxidant performance of the oil can be further improved, the hydrolysis stability and thermal stability can be improved, and the formulated anti-wear hydraulic oil can show more excellent water separation performance.

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

[0022] According to the present invention, the anti-wear hydraulic oil compound is mixed with base oil, pour point depressant, viscosity index agent and anti-foaming agent to obtain high-pressure anti-wear hydraulic oil; base oil, pour point depressant, viscosity index agent and anti-foaming agent can be conventional types in the art. In a preferred embodiment of the present invention, the anti-wear hydraulic oil compound is used to prepare 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 compound is 0.8%, Sinopec II6 base oil is 53%, Sinopec II10 base oil is 46%, polymethacrylate pour point depressant is 0.2%, and composite anti-foaming agent is 50ppm.

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

[0024] The beneficial effect of the present invention is at least that: the present invention selects long-chain primary alkyl zinc thiophosphate, phenolic ester antioxidant, alkyl diphenylamine antioxidant, alkyl phenol calcium sulfide detergent, azole metal deactivator with good oil solubility and weak surface activity, and compounding dinonylnaphthalene sulfonate rust inhibitor with demulsification performance, and the components interact with each other so that the hydraulic oil prepared by the present invention has more outstanding water separation performance, and meets the requirements of anti-wear, anti-oxidation, anti-rust and other performances at the same time. The hydraulic oil composite agent of the present invention does not contain a high molecular weight polyether demulsifier, thereby avoiding the problems of oil turbidity, precipitation and the like caused by the addition of a large amount of demulsifier. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solution and advantages of the embodiments of the invention clearer, the technical solution in the embodiments of the invention is clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the invention, not all of the embodiments. Based on the embodiments of the invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the invention.

[0026] In the following examples, if no specific techniques or conditions are specified, all are carried out according to conventional methods or techniques or conditions described in the literature in the field, or according to the product instructions. The reagents and instruments used, if no manufacturer is specified, are all conventional products that can be purchased through regular channels.

[0027] Unless otherwise stated, the materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0028] In the embodiments of the present invention, the dioctyl zinc dithiophosphate used is dioctyl zinc dithiophosphate T203 purchased from Wuxi Nanfang Petroleum Additives Co., Ltd.; the IRGANOX L135 used is a liquid high molecular weight phenolic antioxidant purchased from BASF; the dinonyl diphenylamine used is KT5535 purchased from Jinzhou Kangtai Lubricant Additives Co., Ltd.; the sulfided alkylphenol calcium used is dioctyl zinc dithiophosphate T121 purchased from Wuxi Nanfang Petroleum Additives Co., Ltd.; the KT5135 used is a phenolic ester type ashless antioxidant purchased from Jinzhou Kangtai Lubricant Additives Co., Ltd.; the dinonylnaphthalene sulfonate used is a sample provided by Anhui Chengtai Chemical Co., Ltd.; the tolyltriazole derivative Irgamet 39 used is purchased from BASF, and other azole metal deactivators used are 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 present invention.

[0030] Example 1

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

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

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

[0034] Example 2

[0035] This embodiment provides an anti-wear hydraulic oil compound with good water separation performance, which is composed of the following components:

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

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

[0038] Example 3

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

[0040] Dioctyl zinc dithiophosphate 55%, KT5135 15%, dinonyl diphenylamine 7%, sulfurized alkyl phenoxide calcium 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 with high water separation performance provided in this embodiment is the same as that in Example 1.

[0042] Example 4

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

[0044] Dioctyl zinc dithiophosphate 65%, IRGANOX L135 8%, dinonyl diphenylamine 2%, sulfurized alkyl phenol calcium 8%, dinonyl naphthalene sulfonate calcium 10%, toluene triazole derivative Irgamet 39 1.0%, thiadiazole derivative T5610.5%, II6 base oil 5.5%.

[0045] Comparative Example 1

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

[0047] Dioctyl zinc dithiophosphate 60%, 2,6-di-tert-butyl-p-cresol 8%, dinonyl diphenylamine 4%, high base synthetic calcium sulfonate T106 6%, dinonyl naphthalene sulfonate zinc 15%, benzotriazole derivative T552 1%, thiadiazole derivative T5611%, II6 base oil 5%.

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

[0049] Comparative Example 2

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

[0051] Dioctyl zinc dithiophosphate 65%, IRGANOX L135 8%, dinonyl diphenylamine 2%, sulfurized alkylphenol calcium 8%, alkenyl succinic acid 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 compound provided in this comparative example is the same as that of 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 dialkyl zinc 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 alkyl phenol calcium, 3 parts of methylbenzotriazole derivatives, and 17 parts of neutral base oil.

[0055] Comparative Example 4

[0056] This comparative example provides a hydraulic oil product compound of a foreign company, which contains 45-55% of dioctyl zinc dithiophosphate, 15-25% of 2,6-di-tert-butylphenol, 3-5% of dinonyl diphenylamine, and 0.5-1 of dinonyl naphthalene sulfonic acid calcium salt.

[0057] Test example

[0058] The anti-wear hydraulic oil composite of the above-mentioned embodiment and comparative example was used to prepare L-HM46 anti-wear hydraulic oil according to a dosage of 0.8% by weight, and performance testing was carried out. The dosage of other components was: 53% of Sinopec II6 base oil, 46% of Sinopec II10 base oil, 0.2% of polymethacrylate pour point depressant, and 50ppm of composite antifoaming agent.

[0059] Basic performance test:

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

[0061] Table 1 Basic performance test

[0062]

[0063]

[0064] The test results in Table 1 show that the performance indicators of the anti-wear hydraulic oil prepared by using the anti-wear hydraulic composite agent of the present invention meet the requirements of GB 11118.1-2011 and have better antioxidant performance and hydrolysis stability.

[0065] Water separation performance comparison test:

[0066] The anti-wear hydraulic oil prepared by the hydraulic oil compound of Examples 1 to 4 of the present invention and Comparative Examples 1 to 4 was tested for its anti-emulsification performance using GB / T7305. The GB / T 7305 standard test method is to load 40 mL of test oil and 40 mL of distilled water into a measuring cylinder, stir for 5 minutes at 54°C or 82°C, and record the time required for the emulsion to be less than 3 mL (the test temperature is 54°C). In order to further evaluate the actual situation of a small amount of water mixed into the hydraulic oil, a ratio of 7:1 was used for the volume of oil and water, 70 mL of oil and 10 mL of water were added to the measuring barrel, and the volume of water separated in 30 minutes was recorded (the test temperature was 54°C). The higher the amount of separated water, the better the water separation performance under the condition of high oil-water ratio. Under the condition of high oil-water ratio, the stability of the formed oil-water emulsion is enhanced, the aggregation and sedimentation rate of water droplets is slowed down, and the difficulty of water separation is increased. The specific results are shown in the table below:

[0067] Table 2 Demulsification performance test

[0068]

[0069]

[0070] The test results in Table 2 show that the anti-wear hydraulic composite of the present invention has obvious advantages in water separation performance. Under standard test conditions (oil-water volume ratio 1:1), the test results of Examples 1 to 4 are better than the national standard requirements, better than Comparative Examples 1 to 3, and equivalent to Comparative Example 4. Under the test conditions of high oil-water ratio (oil-water volume ratio 7:1), Examples 1 to 4 show more obvious advantages in water separation performance than Comparative Examples 1 to 4, and the water separation rate after 30 minutes is not less than 80%, while the water separation rate after 30 minutes of Comparative Examples 1 to 4 is not higher than 50%. Comparative Examples 2 and Comparative Examples 3 are always in an oil-in-water emulsified state, and it is difficult to achieve oil-water separation.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anti-wear hydraulic oil compound with high water separation performance, characterized in that: The invention comprises the following components in parts by weight: 30-80 parts of dialkyl zinc dithiophosphate, 1-20 parts of phenolic ester antioxidant, 1-10 parts of alkyl diphenylamine antioxidant, 1-10 parts of sulfided alkyl phenol calcium detergent, 5-50 parts of dinonylnaphthalene sulfonate rust inhibitor, 1-5 parts of azole metal deactivator and 0-20 parts of base oil.

2. The anti-wear hydraulic oil compound with high water separation performance according to claim 1, characterized in that: The dialkyl zinc dithiophosphate is a long-chain primary alkyl zinc dithiophosphate, preferably dioctyl zinc dithiophosphate T203.

3. The anti-wear hydraulic oil compound with high water separation performance according to claim 1 or 2, characterized in that: The phenolic ester antioxidant is selected from one or more of T512, IRGANOX L135 and KT 5135.

4. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 3, characterized in that: The alkyl diphenylamine antioxidant is selected from one or more of dioctyl diphenylamine, butyl octyl diphenylamine and dinonyl diphenylamine.

5. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 4, characterized in that: The sulfurized alkyl phenate calcium detergent is a sulfurized alkyl phenate calcium T115A with a medium base value or a sulfurized alkyl phenate calcium T115B with a high base value.

6. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 5, characterized in that: The dinonylnaphthalenesulfonate rust inhibitor is selected from one or more of neutral dinonylnaphthalenesulfonate barium, neutral dinonylnaphthalenesulfonate zinc, and neutral dinonylnaphthalenesulfonate calcium, preferably neutral dinonylnaphthalenesulfonate zinc.

7. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 6, characterized in that: The azole metal deactivator is a mixture of one or more of the benzotriazole derivative T552, the tolyltriazole derivative Irgamet 39, and the thiadiazole derivative T561.

8. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 7, characterized in that: The base oil is an API II base oil, preferably, with a viscosity index of 80 to 120, a sulfur content of ≤0.03%, and a saturated hydrocarbon content of>90%.

9. The anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 8, characterized in that: Contains the following ingredients in parts by weight: Preferably, the anti-wear hydraulic oil compound comprises the following components in parts by weight:

10. The method for preparing the anti-wear hydraulic oil compound with high water separation performance according to any one of claims 1 to 9, characterized in that: include: Mix zinc dialkyl dithiophosphate, phenol ester antioxidant, alkyl diphenylamine antioxidant, sulfided alkyl phenol calcium detergent, dinonylnaphthalene sulfonate rust inhibitor, azole metal deactivator and base oil, heat to 50-90°C, stir for 60-300 minutes and filter.

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