CN102399612A - Zinc-free high pressure anti-wear hydraulic oil and preparation method thereof - Google Patents
Zinc-free high pressure anti-wear hydraulic oil and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses zinc-free high pressure anti-wear hydraulic oil. The oil comprises the following components, by mass, 98-99% of base oil, 0.1-1.0% of an antioxidant, 0.2-1.0% of an extreme pressure anti-wear agent, 0.01-0.1% of a rust inhibitor, 0.01-0.1% of a metal passivating agent, 0.01-0.1% of a lustration dispersant and 0.0001-0.001% of an antifoaming agent. The present invention further discloses a preparation method for the zinc-free high pressure anti-wear hydraulic oil. The quality of the hydraulic oil of the present invention meets specification requirements of the anti-wear hydraulic oil superior product in the national standard GB1118.1-94, and can meet specification requirements of the anti-wear hydraulic oil with the highest level Dension HF-0 on the world.
Description
Technical field
The present invention relates to a kind of hydraulicefficiency oil and preparation method thereof, the invention particularly relates to a kind of no zinc High Pressure Antiwear Hydraulic and preparation method thereof.
Background technology
At present; High Pressure Antiwear Hydraulic commonly used has two kinds; Promptly using stable zinc dialkyl dithiophosphate (ZDDP) is the ashless prescription of host for the zinc type prescription of host with sulphur, phosphorus, nitrogen agent; These two kinds of oil property balances have shown advantages of excellent stability in high performance vane pump and plunger pump system, meet Denison HF-0 and Vickers M-2950-S specification, DIN51524 (II) specification and Cincinnati Milascron specification.
For High Pressure Antiwear Hydraulic possesses better wear-resistant, anti-oxidant, emulsion resistance and antirust performance, can add additive usually.Since the seventies, each additive company of the world is developed into the sale of composite additive gradually by the sale of single additive.Composite additive be not merely single agent component adding with, functions such as collaborative, synergy between each additive, hydrotropy are wherein arranged, so the research of composite additive, production, sale have become current additive and developed into new trend.For example, the antiwear hydraulic oil recombiner that Lubrizol company produces has zinc type LZ5178 and Ashless type LZ5186, and the dosage that adds of additive is 1.25% of hydraulicefficiency oil total amount; The antiwear hydraulic oil recombiner that Chevron company produces has zinc type OLOA5660, and the dosage that adds of additive is 1.2% of hydraulicefficiency oil total amount.And the domestic antiwear hydraulic oil recombiner that has Sinopec research institute to produce has low zinc type H5023 and Ashless type H5032, and the dosage that adds of additive is 1.5%～2.0% of hydraulicefficiency oil total amount.The domestic High Pressure Antiwear Hydraulic of several families such as Dalian petrochemical industry, Lanzhou Oil Refinery, Jinxi petrochemical industry and factory of shanghai refinery has in addition been passed through the HPP bench testing of Shanghai Tongji University; Suitable with external like product quality; The existing zinc type of these hydraulicefficiency oil oil dope formulation types; Have ashlessly again, the dosage that adds of additive is 1.0%～1.5% of hydraulicefficiency oil total amount.
Contain the zinc High Pressure Antiwear Hydraulic and be easy to, but difficulty is passed through rampump through vanepump; Because the ZDDP in the prescription produces heavy corrosion to the high-pressure plunger copper facing parts in using, cause hydro-pump to damage; And after sneaking into small amount of moisture in the oil, serious emulsification promptly takes place, cause the obstruction of filtering system.
At present, no zinc antiwear hydraulic oil is a branch of hydraulicefficiency oil, has many not available performances of zinc antiwear hydraulic oil that contain.Prepare no zinc antiwear hydraulic oil and can only adopt ashless extreme pressure anti-wear additives.And mainly there is the problem of two aspects in the selection of ashless extreme pressure anti-wear additives, the one, and hydrolysis stability, the 2nd, extreme pressure anti-wear.A good extreme pressure anti-wear additives not only will have certain extreme pressure property and good resistance to abrasion, and good hydrolysis stability and thermostability will be arranged.The single ashless extreme pressure anti-wear additives of tradition has been difficult to satisfy the requirement of oil property, needs to adopt the compound use of multiple extreme pressure anti-wear additives.
Summary of the invention
First purpose of the present invention aims to provide a kind of no zinc High Pressure Antiwear Hydraulic; This hydraulicefficiency oil has good resistance to emulsion, rust-preventing characteristic, resistance to abrasion, hydrolysis stability, thermostability and filterableness; Oil quality satisfies the specification requirement of the relevant antiwear hydraulic oil premium grads of standard GB 11118.1-94, and can satisfy the specification requirement of antiwear hydraulic oil highest level Dension HF-0 in the world at present.
Second purpose of the present invention provides the preparation method of above-mentioned no zinc High Pressure Antiwear Hydraulic.
The objective of the invention is to realize through following technical measures: a kind of no zinc High Pressure Antiwear Hydraulic, it is characterized in that, comprise following component by mass percent:
In the present invention, be main raw material with the base oil, constitute High Pressure Antiwear Hydraulic with oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent, metal passivator, detergent-dispersant additive and kilfoam.Oxidation inhibitor improves the antioxygen property of product, and its consumption is controlled at 0.1%～1.0% scope, can satisfy the oxidation stability that oil specification requires; Extreme pressure anti-wear additives makes product have good anti-extreme pressure and wear-resistant performance, and its consumption is controlled at 0.2%～1.0% scope, can satisfy the extreme pressure anti-wear that oil specification requires; And rust-preventive agent can form the molecular layer protective film that water molecules is difficult for intrusion through the oil-soluble antirust agent in the metallic surface; This has just been avoided water to contact the possibility that rear oxidation gets rusty with steel surface; The consumption of rust-preventive agent is controlled at the antirust requirement that promptly can satisfy metal in 0.01%～0.1%; And rust-preventive agent can just can not influence the extreme pressure and antiwear behavior of oil product with extreme pressure anti-wear additives contention metallic surface yet.Metal passivator can generate chemical films in the metallic surface; Prevent that metal or metals ion from getting in the oil,, prevent sulphur, the organic acid corrosion surperficial copper to weaken the catalysed oxidn that oil product is produced; Its consumption is controlled in 0.01%～0.1% scope; Promptly satisfy it and suppress active sulphur, the organic acid corrosion surperficial, and can also not influence the extreme pressure and antiwear behavior of oil product with extreme pressure anti-wear additives contention metallic surface to copper.In antiwear hydraulic oil; When adding oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent and metal passivator, also need add in the detergent-dispersant additive and acidic substance that oil product produces during in hydrolysis; Disperse greasy filth; Improve the thermostability of oil product when high temperature, avoid, and generate the non-oil soluble sediment that oil oxidation thing and metallic corrosion oxidation products etc. stop up filter screen because of the non-ferrous metal high temperature corrosion influences the hydraulic unit physical strength.Detergent-dispersant additive has sour neutralization, solubilising, dispersion and cleaning function; And its neutralization, solubilising and dissemination just in time can be improved the thermostability and the hydrolysis stability of High Pressure Antiwear Hydraulic; But if the resistance to emulsion of the excessive reduction hydraulicefficiency oil of peace and quiet dispersive amount that adds, thereby the consumption of detergent-dispersant additive is controlled in 0.01%～0.1% scope.Kilfoam only rises in oil product and eliminates foaming in the oil product, and other performance of oil product is not had synergy, and its content only needs to play the froth breaking effect and gets final product.
The mass percentage content of each component of the present invention is preferably:
Base oil of the present invention is as the basic material of this no zinc High Pressure Antiwear Hydraulic; Preferred hydroisomerization 150SN and the 500SN base oil of adopting; The used hydroisomerization 150SN and the viscosity index of 500SN base oil are less than 120, and stable hydrocarbon is greater than 90%, and sulphur content is less than 0.03%.
Oxidation inhibitor of the present invention adopts phenolic antioxidant or arylamine type inhibitor, is used to improve the thermal oxidation stability of antiwear hydraulic oil.Described phenolic antioxidant comprises DBPC 2,6 ditertiary butyl p cresol (T501), 2,6-di-tert-butylphenol, 4,4-methylene-bis (2,6 di t butyl phenol); Described arylamine type inhibitor comprises N-PA, dialkyl diphenylamine.
Extreme pressure anti-wear additives of the present invention can adopt one or more the mixing in sulfocompound, P contained compound, sulfur phosphorus compound, the sulphur phosphorus-nitrogen compound etc.; The extreme pressure anti-wear additives that is used to improve oilness, reduces friction and the wearing and tearing between the parts and contains active sulphur, phosphorus or nitrogen compound can react with the metallic surface; Generate low sulfuration, phosphatization or the metal nitride solid protective membrane of shearing resistance; Separate two metals, thereby prevented the wearing and tearing and the sintering of metal.Wherein, described sulfocompound can be selected sulfide isobutene (T321), clorafin (T302) etc. for use, and the abrasion resistance of this type of extreme pressure anti-wear additives is good, and the corrosion to copper in the hydrolysis stability test also relaxes, and the hydrolysis acid number is also lower.Described P contained compound can be selected tritolyl phosphate (T306), di-n-butyl phosphite (T304) etc. for use; Described sulfur phosphorus compound can be selected triphenyl-thiophosphate (T309), the multiple ester amine salt (T307B) of thiophosphoric acid, thiophosphatephosphorothioate (T311) etc. for use; Described sulphur phosphorus-nitrogen compound can be selected the nitrogenous verivate of sulphur phosphoric acid (T305), the multiple ester amine salt (T307) of thiophosphoric acid etc. for use.
Rust-preventive agent of the present invention can adopt one or more mixtures in sulphonate, carboxylic acid and the carboxylate salt etc., is used to prevent that the corrosion problem from appearring in hydraulicefficiency system and parts.Wherein, described sulphonate can preferred neutral dinonyl naphthalene sulfonate barium (T705A), alkaline dinonyl naphthalene sulfonate barium (T705) etc., and described carboxylic acid can be selected dodecenylsuccinic acid (T746) for use, and described carboxylate salt can be selected petroleum oxidate ester barium salt (T743) etc. for use.
Metal passivator of the present invention can adopt 124 Triazole and verivate or thiadiazoles derivative, is used to prevent the catalysis booster action of metals ion to the autoxidation of lubricating oil.Wherein, Described 124 Triazole and verivate thereof be N preferably; N-dialkyl amido methylene-benzene triazole (T551), liquid benzene triazole derivative (Irgamet 30), the affixture that obtains through addition reaction by 124 Triazole and organic acid acetic: 124 Triazole metalloid passivator (AD-12) etc., described thiadiazoles derivative can be selected thiadiazoles derivative (T561) or 2 for use, 5-dimercapto-1; 3,4-thiadiazoles derivative (Cuvan 484) etc.
Detergent-dispersant additive of the present invention can adopt high base number calcium mahogany sulfonate or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER etc., is used for improving the generation of the greasy filth of heat stability test, improves the hydrolysis stability of oil product.Wherein, described high base number calcium mahogany sulfonate or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER are meant calcium mahogany sulfonate or the calcium sulfenyl phenolate of its base number greater than 200mgKOH/g.High base number calcium mahogany sulfonate of the present invention is high base number calcium mahogany sulfonate (T103), high base number calcium alkylbenzenesulfonate (T106) etc. preferably, and described SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER can be selected calcium sulfenyl phenolate (P52) or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (LZ6500) etc. for use.
Kilfoam of the present invention can adopt siliceous kilfoam or non-silicon kilfoam etc., is used for eliminating the bubble that the antiwear hydraulic oil use produces.Wherein, described siliceous kilfoam is dimethyl silicone oil (T901) etc. preferably, and described non-silicon kilfoam can be selected propenoate and ether copolymer (T911) or propenoate and ether copolymer (T912) etc. for use.
Second purpose of the present invention realizes through following technical measures: a kind of preparation method of above-mentioned no zinc High Pressure Antiwear Hydraulic; It is characterized in that; Earlier base oil is heated to 50～60 ℃; Add oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent, metal passivator, detergent-dispersant additive and kilfoam then and stir, filter, can obtain not having zinc High Pressure Antiwear Hydraulic finished product.
Compared with prior art, the present invention has following beneficial effect:
(1) hydraulicefficiency oil provided by the invention is mixed and made into by base oil and oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent, metal passivator, detergent-dispersant additive and kilfoam; Do not contain zinc in the hydraulicefficiency oil; Have good resistance to emulsion, rust-preventing characteristic, resistance to abrasion, hydrolysis stability, thermostability and filterableness; Oil quality satisfies in the standard GB 11118.1-94 antiwear hydraulic oil specification requirement to premium grads; Pass through graduate T5D vanepump of Dalian Petrochemical Industry Company and the bench testing of P46 rampump HPP, can satisfy at present antiwear hydraulic oil highest level Dension HF-0 specification in the world.
(2) hydraulicefficiency oil provided by the invention is no zinc antiwear hydraulic oil; Oxidation inhibitor wherein, extreme pressure anti-wear additives, rust-preventive agent, metal passivator, detergent-dispersant additive and kilfoam constitute composite additive; Mass percentage content in hydraulicefficiency oil is 0.3301～2.301%; This mass percentage content also is that composite additive adds dosage in hydraulicefficiency oil, with the existing composite additive that the zinc antiwear hydraulic oil arranged to add dosage suitable, even its minimum dosage that adds is lower than 1%.
(3) hydraulicefficiency oil composite additive provided by the invention to add dosage few, have good abrasion resistance, reduced production cost, have high cost performance.
Embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is set forth, yet protection scope of the present invention is not only to be confined to following examples.The those of ordinary skill of affiliated technical field all can be realized the object of the invention according to content disclosed by the invention.
Embodiment one:
(1) earlier 985 kilograms hydroisomerization 150SN is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 5 kilograms of T309,2 kilograms of T501,3 kilograms of T306,0.5 kilogram of AD-12,0.6 kilogram of T705,0.3 kilogram of P52 (base number is 300mgKOH/g), 0.003 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Embodiment two:
(1) earlier 985 kilograms hydroisomerization 500SN is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 5 kilograms of T309,2 kilograms of T501,3.5 kilograms of T306,0.5 kilogram of T551,0.6 kilogram of T705A, 0.5 kilogram of P52 (base number is 300mgKOH/g), 0.003 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Embodiment three:
(1) earlier 985 kilograms hydroisomerization 500SN is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 6 kilograms of T309,3 kilograms of T501,2 kilograms of T306,0.6 kilogram of T561,0.5 kilogram of T705A, 0.3 kilogram of P52 (base number is 300mgKOH/g), 0.002 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Embodiment four:
(1) earlier 985 kilograms hydroisomerization 150SN is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 2 kilograms of T305,2 kilograms of T501,6 kilograms of T306,0.8 kilogram of T561,0.6 kilogram of T705A, 0.3 kilogram of T106 (base number is 295mgKOH/g), 0.003 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Embodiment five:
(1) earlier 985 kilograms hydroisomerization 500SN is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 6 kilograms of T309,2 kilograms of T501,3 kilograms of T306,0.5 kilogram of T551,0.4 kilogram of T746,0.5 kilogram of P52 (base number is 300mgKOH/g), 0.003 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Embodiment six:
(1) earlier 985 kilograms hydroisomerization 150SN base oil is placed reaction kettle, heat temperature raising to 50 ℃～60 ℃;
(2) add 5 kilograms of T309,2 kilograms of T501,3 kilograms of T306,0.5 kilogram of T561,0.6 kilogram of T705A, 0.3 kilogram of T106 (base number is 295mgKOH/g), 0.003 kilogram of T901; Mix 20min～30min; Get mixture, promptly getting does not have the zinc High Pressure Antiwear Hydraulic.
Following table has been listed the analytical results with the embodiment of the invention three, four and six.Visible by table 1; Quality of the present invention satisfies among the standard GB 11118.1-94 32,46 and the requirement of the premium grads of 68 3 kind of specification antiwear hydraulic oil; And through domestic HPP bench testing; Be bench testing of T5D vanepump and the bench testing of Denison P46 rampump, oil quality has reached Dension HF-0 specification requirement.
Table 1 the present invention and 32,46 and 68 3 kind of specification antiwear hydraulic oil comparative analysis result
Claims (10)
1. a no zinc High Pressure Antiwear Hydraulic is characterized in that, comprises following component by mass percent:
2. no zinc High Pressure Antiwear Hydraulic according to claim 1 is characterized in that the mass percentage content of each component is:
3. no zinc High Pressure Antiwear Hydraulic according to claim 1 and 2 is characterized in that, the mixing of one or both in described base oil employing hydroisomerization 150SN and the 500SN base oil.
4. no zinc High Pressure Antiwear Hydraulic according to claim 3 is characterized in that, described oxidation inhibitor adopts phenolic antioxidant or arylamine type inhibitor; The mixing of one or more in described extreme pressure anti-wear additives employing sulfocompound, P contained compound, sulfur phosphorus compound, the sulphur phosphorus-nitrogen compound; Described rust-preventive agent adopts sulphonate or carboxylic acid and carboxylate salt; Described metal passivator adopts 124 Triazole and verivate or thiadiazoles derivative; Described detergent-dispersant additive adopts high base number calcium mahogany sulfonate or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER; Described kilfoam adopts siliceous kilfoam or non-silicon kilfoam.
5. no zinc High Pressure Antiwear Hydraulic according to claim 4 is characterized in that, described phenolic antioxidant adopts DBPC 2,6 ditertiary butyl p cresol, 2,6-di-tert-butylphenol and 4, the mixing of one or both in the 4-methylene-bis (2, the 6-di-tert-butylphenol); The mixing of one or both in described arylamine type inhibitor employing N-PA and the dialkyl diphenylamine.
6. no zinc High Pressure Antiwear Hydraulic according to claim 4 is characterized in that, described sulfocompound adopts with sulfide isobutene or clorafin; Described P contained compound adopts tritolyl phosphate or di-n-butyl phosphite; Described sulfur phosphorus compound adopts triphenyl-thiophosphate, the multiple ester amine salt of thiophosphoric acid or thiophosphatephosphorothioate; Described sulphur phosphorus-nitrogen compound adopts nitrogenous verivate of sulphur phosphoric acid or the multiple ester amine salt of thiophosphoric acid.
7. no zinc High Pressure Antiwear Hydraulic according to claim 4; It is characterized in that; Described sulphonate adopts neutral dinonyl naphthalene sulfonate barium or alkaline dinonyl naphthalene sulfonate barium, and described carboxylic acid and carboxylate salt adopt dodecenylsuccinic acid or petroleum oxidate ester barium salt.
8. no zinc High Pressure Antiwear Hydraulic according to claim 4 is characterized in that, described 124 Triazole and verivate thereof adopt N, N-dialkyl amido methylene-benzene triazole, liquid benzene triazole derivative or 124 Triazole metalloid passivator; Described thiadiazoles derivative adopts thiadiazoles derivative or 2,5-dimercapto-1,3,4-thiadiazoles derivative.
9. no zinc High Pressure Antiwear Hydraulic according to claim 4 is characterized in that, described high base number calcium mahogany sulfonate adopts high base number calcium mahogany sulfonate or high base number calcium alkylbenzenesulfonate; Described SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER adopts calcium sulfenyl phenolate or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER.
10. the preparation method of the described no zinc High Pressure Antiwear Hydraulic of the arbitrary claim of claim 1～9; It is characterized in that; Earlier base oil is heated to 50～60 ℃; Add oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent, metal passivator, detergent-dispersant additive and kilfoam then and stir, filter, promptly obtain not having zinc High Pressure Antiwear Hydraulic finished product.
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| CN102925263A (en) * | 2012-10-30 | 2013-02-13 | 武汉博达特种润滑技术有限公司 | Ultrahigh viscosity index anti-wear hydraulic oil and preparation method thereof |
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| CN102994195A (en) * | 2012-11-12 | 2013-03-27 | 关子杰 | Extreme pressure, wear resisting and friction reducing additive for lubricating oil |
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| CN104342229A (en) * | 2013-07-26 | 2015-02-11 | 中国石油化工股份有限公司 | Biodegradable hydraulic oil composition |
| CN105985833A (en) * | 2015-01-29 | 2016-10-05 | 中国石油天然气股份有限公司 | Zinc-free hydraulic oil additive composition |
| CN104927987A (en) * | 2015-05-19 | 2015-09-23 | 福建省天猫石油化工有限公司 | Colorless high-pressure and long-life anti-wear hydraulic oil and preparation method thereof |
| CN106947570A (en) * | 2017-04-07 | 2017-07-14 | 深圳市前海龙达新能源有限公司 | A kind of antiwear hydraulic oil and preparation method thereof |
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