Flame-retardant hydraulic oil, method for producing same, and use thereof

Abstract

The present application relates to the technical field of hydraulic oil, and discloses a fire-retardant hydraulic oil, wherein the hydraulic oil comprises base oil, antioxidant, copper corrosion inhibitor, rust inhibitor, antifoaming agent, demulsifier and hydrolysis inhibitor; wherein the base oil is selected from at least one of mixture A, mixture B and mixture C; wherein the mixture A is selected from a compound as shown in general formula (I): wherein X is selected from any one of, and the mixture B and the mixture C both comprise (4-tert-butylphenyl) diphenyl phosphate, bis(4-tert-butylphenyl) phenyl phosphate, tris(4-tert-butylphenyl) phosphate and triphenyl phosphate. The hydraulic oil has excellent antioxidant, corrosion / rust resistance, emulsion resistance, hydrolysis resistance, antifoaming performance and accelerated aging resistance, slows down the deterioration speed of triaryl phosphate fire-retardant hydraulic oil, and prolongs the service life of the fire-retardant oil.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydraulic oil, and particularly relates to a flame-retardant hydraulic oil and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of the power industry, more and more large-capacity and high-parameter steam turbine units are put into operation. In order to pursue higher power generation efficiency and safety, the electro-hydraulic control system of the steam turbine has generally adopted triaryl phosphate ester type flame-retardant hydraulic oil as the hydraulic working medium. The triaryl phosphate ester flame-retardant hydraulic oil has excellent anti-flame performance, but in the presence of high temperature, high pressure, water, air, ferrous metals and non-ferrous metals, the triaryl phosphate ester will deteriorate to generate acidic phosphate ester, alkyl phenol and other degradation products. These decomposition products cause the use characteristics of the hydraulic oil to deteriorate, form deposits, and accelerate the corrosion of sensitive components of the oil system.

[0003] CN110305722A discloses a phosphate ester anti-flame hydraulic oil, raw materials include, by weight percentage, 0.8-1.0 % of an antioxidant, 0.4-0.6 % of a rust inhibitor, 0.8-1.0 % of a hydrolysis stability enhancer, 4.0-6.0 % of an acid value improver, 0.2-1.0 % of an anti-electric corrosion agent, 100-150 ppm of an anti-foaming agent, and the balance is a phosphate ester base liquid. The prepared hydraulic oil phosphate ester anti-flame hydraulic oil product has excellent anti-foaming property, low chlorine content, low acid value, high self-ignition point, high resistivity, low air release value, excellent hydrolysis stability and low particle contamination, but the anti-corrosion, rust prevention, anti-hydrolysis, anti-emulsification and other performances are not detected, and the hydrolysis stability enhancer used in the application is 3,5-di-tert-butyl-4-hydroxybenzene propionic acid methyl ester, ethoxylated-1,6-hexanediol beef tallow alkyl quaternary amine sulfate and N,N-dialkyl amino methylene benzene triazole mixed in a mass ratio of 5:2:3, which is different from the components and their addition ratios in the present application.

[0004] In summary, the hydraulic oil needs to have good anti-oxidation, anti-corrosion, anti-emulsification, anti-hydrolysis, anti-foaming and anti-aging properties, slow down the deterioration rate of the triaryl phosphate ester flame-retardant hydraulic oil, prolong the service life of the anti-flame oil, and ensure the low-cost and safe operation of large steam turbine units of thermal power and nuclear power. However, the commercial hydraulic oil cannot fully meet the requirements, and there is an urgent need to provide a suitable product. SUMMARY

[0005] The present application aims to overcome the problems of poor anti-oxidation, anti-corrosion, rust prevention, anti-emulsification, anti-hydrolysis, anti-foaming and anti-aging properties and short TOST oxidation life of the existing hydraulic oil, and provides a flame-retardant hydraulic oil and a preparation method and application thereof.

[0006] In order to achieve the above-mentioned purpose, the present application provides a fire-retardant hydraulic oil in a first aspect, wherein the hydraulic oil comprises base oil, antioxidant, copper corrosion inhibitor, antirust agent, antifoam agent, demulsifier and anti-hydrolysis agent;

[0007] The base oil is selected from at least one of mixture A, mixture B and mixture C.

[0008] The mixture A is selected from a compound as shown in general formula (I):

[0009]

[0010] X is selected from

[0011]

[0012] The mixture B and the mixture C each comprise (4-tert-butylphenyl) diphenyl phosphate, di(4-tert-butylphenyl) phenyl phosphate, tri(4-tert-butylphenyl) phosphate and triphenyl phosphate.

[0013] The present application provides a preparation method of fire-retardant hydraulic oil in a second aspect, wherein the method comprises mixing triaryl phosphate base oil, antioxidant, copper corrosion inhibitor, antirust agent, antifoam agent and demulsifier.

[0014] Preferably, the mixing conditions comprise a temperature of 80-100℃, a pressure of-0.099MPa to-0.096MPa and a time of 1-2h.

[0015] The present application provides a fire-retardant hydraulic oil prepared by the fire-retardant hydraulic oil of the first aspect or the method of the third aspect in a third aspect.

[0016] Through the above technical solution, the present application achieves the following technical effects:

[0017] The present application provides a triaryl phosphate type fire-retardant hydraulic oil composition, which can maximize the synergistic effect between components, improve the antioxidant, corrosion / antirust, emulsification, hydrolysis, antifoam and accelerated aging properties of the fire-retardant hydraulic oil, slow down the deterioration speed of the triaryl phosphate fire-retardant hydraulic oil, prolong the service life of the fire-retardant oil, and provide a practical solution for the safe operation and low-cost operation and maintenance of large steam turbine units of thermal power and nuclear power. DETAILED DESCRIPTION

[0018] ​The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values from the lower value to the upper value, inclusive of both values, and to also include any value approximately or about the value. For numeric ranges, the endpoints are combined with the individual points to form new numeric ranges that are considered disclosed herein.

[0019] The first aspect of the present application provides a fire-retardant hydraulic oil, wherein the hydraulic oil comprises base oil, antioxidant, copper corrosion inhibitor, rust inhibitor, antifoam agent, demulsifier and anti-hydrolysis agent;

[0020] The base oil is selected from at least one of mixture A, mixture B and mixture C.

[0021] The mixture A is selected from the compound as shown in general formula (I):

[0022]

[0023] X is selected from

[0024]

[0025] The mixture B and the mixture C each comprise (4-tert-butylphenyl) diphenyl phosphate, bis(4-tert-butylphenyl) phenyl phosphate, tris(4-tert-butylphenyl) phosphate and triphenyl phosphate.

[0026] In the present application, the corrosion inhibitor is a compound capable of reducing the corrosion rate of metal, which forms a passivation layer on the surface of the metal to prevent the metal from being corroded. The antifoam agent can be adsorbed on the bubble membrane after contacting the bubble membrane, and then immersed into the membrane, so that the surface tension of the part is significantly reduced, while the rest of the membrane surface still maintains the original larger surface tension. The difference in surface tension on the bubble membrane leads to the rupture of the bubble membrane. The demulsifier can destroy the emulsified liquid structure to achieve the purpose of separating the phases in the emulsion. The anti-hydrolysis agent has a molecular structure containing active groups (such as carbodiimide or polycarbodiimide groups). The carbodiimide group has high reactivity with carboxyl groups and generates a stable urea-based compound. By using the characteristics of carbodiimide, the carboxyl groups that easily cause autocatalytic hydrolysis of polyester materials can be eliminated, and the molecular chain breakage and comprehensive property decline caused by hydrolysis of phosphoric acid ester can be effectively inhibited.

[0027] ​In the present application, the mixture A can be obtained by a self-made method, and the specific preparation method comprises the following steps: reacting at least one of dimethylphenol, ethylphenol and phenol isomers with phosphoryl chloride under the action of a catalyst (at least one selected from aluminum chloride, magnesium chloride and calcium chloride), and refining the reaction product to obtain the mixture A, and the reaction process is as follows:

[0028]

[0029] In the present application, the mixture A is a complex mixture, which comprises a compound selected from the compounds shown in the general formula (I); for X in the formula (I), the following structures can be taken, X has a substituted or unsubstituted alkyl group, wherein the wavy line represents the position of X structure connected with oxygen in the formula (I), wherein X is dimethylphenyl and / or ethylphenyl and / or methylphenyl and / or trimethylphenyl and / or phenyl, specifically: X is 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 1-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,4,5-trimethylphenyl, phenyl.

[0030] In the present application, the hydrolysis product of the mixture A comprises at least one of 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 3-ethylphenol, 4-ethylphenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 3,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2,4,5-trimethylphenol and phenol. The composition and content of the mixture A are determined by measuring the composition and content of the hydrolysis product in the mixture A, wherein the composition and content of the hydrolysis product of the mixture A are determined by using a gas chromatograph, and the instrument model is 7890B.

[0031] In the present application, the mixture B can be obtained by a self-made method, and the preparation process is divided into two steps: (1) preparing tert-butylphenol by alkylating butene with p-phenol; (2) reacting tert-butylphenol with phenol and phosphoryl chloride under the action of a catalyst (at least one selected from aluminum chloride, magnesium chloride and calcium chloride), and refining the reaction product to obtain the mixture B, and the reaction process is as follows:

[0032]

[0033] According to some embodiments of the present application, the mass ratio of (4-tert-butylphenyl) diphenyl phosphate, di(4-tert-butylphenyl) phenyl phosphate, tri(4-tert-butylphenyl) phosphate and triphenyl phosphate in the mixture B is (74-84):(16-24):(0.1-1):(0.1-1).

[0034] In the present application, the mixture C can be obtained by a self-made method, and the specific preparation method comprises: performing an ester exchange reaction on triphenyl phosphate and p-tert-butylphenol to obtain the mixture C, and the reaction process is as follows:

[0035]

[0036] According to some embodiments of the present application, the mass ratio of (4-tert-butylphenyl) diphenyl phosphate, di(4-tert-butylphenyl) phenyl phosphate, tri(4-tert-butylphenyl) phosphate and triphenyl phosphate in the mixture C is (76-81):(16-20):(0.2-3):(0.2-3).

[0037] In the present application, the components contained in the mixture B and the mixture C are the same, but the specific content of the components is different, thereby providing the hydraulic oil solving the technical problem of the present application.

[0038] In the present application, the hydrolysis product of the mixture B or C includes tert-butylphenol and phenol, and the composition and content of the mixture B or C are determined by determining the composition and content of the hydrolysis product of the mixture B or C, wherein the content of the hydrolysis product is determined by using a gas chromatograph with a model number of 7890B.

[0039] In the present application, when the types of the mixtures A, B and C meet the above range, the 50℃ kinematic viscosity of the base oil can be adjusted to be between 23-33 mm 2 / s, and the hydrolysis resistance of the base oil itself can be optimized.

[0040] According to some embodiments of the present application, the residual amount of dimethylphenol in the base oil is ≤0.1wt%, the acid value is ≤0.03mgKOH / g, the water-soluble acid pH is 5.6-8, the density at 20℃ is 1.13-1.17g / cm 3 , the kinematic viscosity at 50℃ is ≥23 mm 2 / s, the self-ignition point is ≥530℃, the air release value at 50℃ is ≤4min, the flash point is ≥245℃, the foam characteristics at 24℃ are ≤10mL / 0mL, and the resistivity at 20℃ is ≥2×10 10 Ω·cm.

[0041] In the present application, when the base oil has the above properties, the stability of the product performance after compounding with additives can be improved.

[0042] According to some embodiments of the present application, the content of the base oil is 91.5-99.35wt% based on the total mass of the hydraulic oil; the content of the antioxidant is 0.53-3wt%; the content of the copper corrosion inhibitor is 0.005-1wt%, preferably 0.008-0.03wt%; the content of the rust inhibitor is 0.005-0.2wt%, preferably 0.008-0.03wt%; the content of the antifoam agent is 0.005-0.1wt%, preferably 0.005-0.05wt%; the content of the demulsifier is 0.005-0.2wt%, preferably 0.03-0.1wt%; and the content of the hydrolysis inhibitor is 0.1-4wt%, preferably 0.5-2wt%.

[0043] In the present application, when the contents of the base oil, antioxidant, copper corrosion inhibitor, rust inhibitor, antifoam agent, demulsifier and hydrolysis inhibitor meet the above ranges, the synergistic effect between the components can be maximized, the anti-oxidation, anti-corrosion / rust, anti-emulsification, anti-hydrolysis, anti-foaming and anti-accelerated aging properties of the flame-retardant hydraulic oil can be improved, the deterioration rate of the triaryl phosphate flame-retardant hydraulic oil can be slowed down, and the service life of the flame-retardant oil can be prolonged.

[0044] According to some embodiments of the present application, the antioxidant is selected from at least one of 2,2,4-trimethyl-1,2-dihydroquinoline dimer, octyl butyl diphenylamine, 4,6-bis(octylthiomethyl) o-cresol, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 2,2'-methylenebis-(4-methyl-6-tert-butylphenol).

[0045] In the present application, when the types of the antioxidants meet the above defined ranges, the synergistic effect of the individual antioxidants can be exerted, and especially when the amine antioxidant is compounded with the phenolic antioxidant, the TOST oxidation life of the triaryl phosphate can be significantly improved.

[0046] According to some embodiments of the present application, the copper corrosion inhibitor is selected from at least one of N,N'-disalicylidene-1,2-propanediamine aminopropane, 2-mercaptobenzothiazole, benzotriazole, methylbenzotriazole, carboxybenzotriazole, N,N'-di(2-ethylhexanoic acid)-methyl-1H-benzotriazole-1-methylamine, 1,3,4-thiadiazole-2,5-dithiododecyl ester and 1,3,4-thiadiazole-2,5-dithiohexadecyl ester.

[0047] In the present application, when the kind of the copper corrosion inhibitor meets the above-mentioned limited range, the copper corrosion inhibitor can be chemically adsorbed with active copper atoms or copper ions on the surface of the metal copper, and then chelation occurs to form a dense and firm protective film, which can well protect the copper. The protective film can effectively isolate the copper surface from water, oxygen and other corrosive substances, thereby slowing down the corrosion process of the copper component. This protective effect can improve the service life and reliability of the hydraulic system elements.

[0048] According to some embodiments of the present application, the rust inhibitor is selected from at least one of 1-aminoethyl-2 (heptadecenyl) imidazoline dodecyl succinate, dodecyl succinate methyl ester, oleoyl sarcosine, oleoyl amino alkyl amine and imidazoline alcohol.

[0049] In the present application, when the kind of the rust inhibitor meets the above-mentioned limited range, the rust inhibitor can chemically react with the metal surface to form a passivation film which is difficult to dissolve in water. This passivation film can effectively isolate the metal surface from water, oxygen and other corrosive substances, thereby effectively slowing down the corrosion process of the metal component. This protective effect can prolong the service life of the hydraulic system elements and improve their reliability.

[0050] According to some embodiments of the present application, the anti-foaming agent is selected from at least one of polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane.

[0051] Preferably, the anti-foaming agent comprises polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane.

[0052] Preferably, the polydimethylsiloxane has a kinematic viscosity of 350-1000 mm 2 / s at 25°C.

[0053] Preferably, the trifluoropropyl silicone oil has a kinematic viscosity of 8000-10000 mm 2 / s at 25°C.

[0054] Preferably, the polyacrylate has a kinematic viscosity of 90-180 mm 2 / s at 25°C.

[0055] Preferably, the polydiethylsiloxane has a kinematic viscosity of 2.8-4.8 mm 2 / s at 200°C.

[0056] More preferably, the mass ratio of the polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane is (0.1-0.6):(0.01-0.1):(0.01-0.1):(0.5-0.9), preferably (0.3-0.5):(0.01-0.03):(0.01-0.03):(0.6-0.9).

[0057] In the present application, when the types of the anti-foaming agent meet the above-mentioned limited range, the polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane are compounded in a specific ratio to achieve synergistic defoaming effect. The defoaming agent system with this specific composition not only has excellent anti-foaming performance, but also has excellent anti-filtering properties, and is particularly suitable for controlling the foam properties of mixed base oil systems. Among them, the polydimethylsiloxane, polyacrylate and trifluoropropyl silicone oil can play a synergistic defoaming effect by compounding, and the polydiethylsiloxane plays a role of dissolving, dispersing and stabilizing the above-mentioned components. The defoaming agent system with this specific composition greatly improves the performance and effect of the lubricating oil defoaming agent.

[0058] In the present application, the polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane in the anti-foaming agent can be obtained by purchase, such as polydimethylsiloxane from Dow Chemical Company, product model XIAMETER PMX-200 silicone oil; trifluoropropyl silicone oil from Shanghai Yucheng Chemical Co., Ltd., product model RN 150FS; polyacrylate from Mingling Chemical, Germany, product model FOAM BAN 3633E; polydiethylsiloxane from Alatai Chemical Co., Ltd., product model No. 3 ethyl silicone oil. TM PMX-200 silicone oil; trifluoropropyl silicone oil from Shanghai Yucheng Chemical Co., Ltd., product model RN 150FS; polyacrylate from Mingling Chemical, Germany, product model FOAM BAN 3633E; polydiethylsiloxane from Alatai Chemical Co., Ltd., product model No. 3 ethyl silicone oil.

[0059] According to some embodiments of the present application, the demulsifier comprises polyoxyethylene polyoxypropylene polyether and diamine propylene oxide polymer.

[0060] Preferably, the 100℃ kinematic viscosity of the polyoxyethylene polyoxypropylene polyether is 10-16mm 2 / s.

[0061] Preferably, the 100℃ kinematic viscosity of the diamine propylene oxide polymer is 14-23mm 2 / s.

[0062] Preferably, the mass ratio of the polyoxyethylene polyoxypropylene polyether and diamine propylene oxide polymer is (0.5-0.7):(0.1-0.6).

[0063] In the present application, the polyoxyethylene polyoxypropylene polyether and the diamine propylene oxide polymer in the demulsifier can be purchased on the market, such as the polyoxyethylene polyoxypropylene polyether purchased from Shanghai Yucheng Chemical Co., Ltd., product model Enable394; the diamine propylene oxide polymer purchased from Jinzhou Shengda Chemical Co., Ltd., product model T-1001.

[0064] In the present application, when the demulsifier meets the above-mentioned limited range, the demulsifier can separate oil and water by using its surface activity through wetting, penetration and emulsification. Specifically, the lipophilic group in the demulsifier molecule will interact with the oil molecules in the lubricating oil, and the hydrophilic group will interact with the water molecules. When the demulsifier is added to the lubricating oil, they will be adsorbed on the oil-water interface, reduce the interfacial tension, and weaken the interaction force between water and oil, so as to realize the separation of oil and water.

[0065] According to some embodiments of the present application, the anti-hydrolysis agent includes at least one of neopentyl glycol diglycidyl ether, butyl epoxy soyate, oxazoline derivative, N,N'-di(2,6-diisopropylphenyl)carbodiimide, triethanolamine and alkyl diphenylamine.

[0066] Preferably, the anti-hydrolysis agent includes neopentyl glycol diglycidyl ether, butyl epoxy soyate, oxazoline derivative, N,N'-di(2,6-diisopropylphenyl)carbodiimide, triethanolamine and alkyl diphenylamine.

[0067] More preferably, the mass ratio of the neopentyl glycol diglycidyl ether, butyl epoxy soyate, oxazoline derivative, N,N'-di(2,6-diisopropylphenyl)carbodiimide, triethanolamine and alkyl diphenylamine is (0.2-5):(0.05-5):(0.005-2):(0.005-3):(0.005-1):(0.05-4).

[0068] In the present application, when the anti-hydrolysis agent meets the above-mentioned limited range, the anti-hydrolysis agent composition can react with the acidic groups in the system, reverse the hydrolysis equilibrium, thereby playing an anti-hydrolysis role. For example, the -N=C=N- functional group in N,N'-di(2,6-diisopropylphenyl)carbodiimide can be coupled with a phosphoric acid hemiester to generate a structure similar to an ureide, thereby playing a role in inhibiting hydrolysis; the unstable cyclic structure in epoxy soybean oil acid butyl ester and oxazoline derivatives can undergo ring-opening reaction with phosphate groups to reduce the acidic groups in the system, thereby playing an anti-hydrolysis role. Neopentyl glycol diglycidyl ether utilizes its chemical reaction with acidic substances to generate the corresponding acid or salt, thereby capturing and removing the acidic substances; the amino or imino groups in triethanolamine and alkyl diphenylamine can react with anionic groups such as carboxyl and phosphoric acid groups to generate stable complexes, thereby preventing the hydrogen bonding between water molecules and anionic groups, and enhancing the hydrolysis stability of lubricating oil. The anti-hydrolysis agents with different mechanisms of action are compounded according to the above-mentioned limited range, which can enhance the sensitivity of various components or isomers in mixtures A, B and C, and enhance the adaptability of the formula system.

[0069] The second aspect of the present application provides a preparation method of a fire-retardant hydraulic oil, wherein the method comprises: mixing triaryl phosphate ester base oil, antioxidant, copper corrosion inhibitor, antirust agent, antifoaming agent and demulsifier.

[0070] Preferably, the mixing conditions comprise: temperature of 80-100℃, pressure of-0.099MPa to-0.096MPa, and time of 1-2h.

[0071] The third aspect of the present application provides the use of the fire-retardant hydraulic oil prepared by the fire-retardant hydraulic oil of the first aspect or the method of the second aspect in a steam turbine.

[0072] According to a particularly preferred embodiment of the present application, there is provided a method for preparing a fire-retardant hydraulic oil, which comprises: mixing a base oil (selected from at least one of mixture A, mixture B and mixture C), an antioxidant (specifically a mixture of 2,2,4-trimethyl-1,2-dihydroquinoline dimer, octyl butyl diphenylamine, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), a copper corrosion inhibitor (specifically a mixture of methylbenzotriazole and N,N-di(2-ethylhexyl)-1H-methylbenzotriazole-1-methylamine), a rust inhibitor (specifically a mixture of dodecenyl succinic acid methyl ester and oleoyl sarcosine), an antifoaming agent (a mixture prepared according to a mass ratio of polydimethylsiloxane:trifluoropropyl silicone oil:polyacrylate:polydiethylsiloxane being (0.3-0.5):(0.01-0.03):(0.01-0.03):(0.6-0.9), wherein the polydimethylsiloxane has a kinematic viscosity at 25°C of 350-1000 mm 2 / s, the trifluoropropyl silicone oil has a kinematic viscosity at 25°C of 8000-10000 mm 2 / s, the polyacrylate has a kinematic viscosity at 25°C of 90-180 mm 2 / s, and the polydiethylsiloxane has a kinematic viscosity at 200°C of 2.8-4.8 mm 2 / s), a demulsifier (prepared according to a mass ratio of polyoxyethylene polyoxypropylene polyether:diamine propylene oxide polymer being (0.5-0.7):(0.1-0.6)), and an anti-hydrolysis agent (prepared according to a mass ratio of neopentyl glycol diglycidyl ether:butyl epoxy soyate:oxazoline derivative:N,N'-di(2,6-diisopropylphenyl)carbodiimide:triethanolamine:alkyl diphenylamine being (0.2-5):(0.05-5):(0.005-2):(0.005-3):(0.005-1):(0.05-4)), stirring uniformly, dehydrating at 80-100°C and -0.099 MPa to -0.096 MPa for 1-2 h, to obtain the fire-retardant hydraulic oil.

[0073] In order to further illustrate the present application, the following examples are provided in detail.

[0074] The dimethylphenol residue of the base oil and the phenol composition are determined according to a gas chromatography method, and the instrument model is Agilent 7890B.

[0075] The acid value of the base oil is determined according to GB / T 264, and the instrument model is BF-41.

[0076] The water-soluble acid of the base oil is determined according to GB / T 259, and the instrument model is ZD-2.

[0077] The density of the base oil was determined according to GB / T 1884, instrument model 0760.

[0078] The kinematic viscosity of the base oil was determined according to NB / SH / T 0870, instrument model SVM3001.

[0079] The auto-ignition point of the base oil was determined according to DL / T 706, instrument model ZHR402.

[0080] The air release value of the base oil was determined according to SH / T 0308, instrument model 15850-5.

[0081] The flash point of the base oil was determined according to GB / T 3536, instrument model BF-01A.

[0082] The foam characteristics of the base oil were determined according to GB / T 12579, instrument model BF-24.

[0083] The resistivity of the base oil was determined according to GB / T 5654, instrument model Megger OTD.

[0084] In the following examples, all raw materials are commercially available unless otherwise specified.

[0085] Preparation Example 1

[0086] A mixture of 61 parts of a mixture of C1+C3 phenols (containing 3-methylphenol, trimethylphenol), 599 parts of a mixture of C2 phenols (containing 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 3-ethylphenol, 4-ethylphenol) was mixed and heated to substantially melt, then 9.0 parts of aluminum chloride was added and stirred, 248.68 parts of phosphorus oxychloride was added when the temperature dropped to 50°C, gradually heated to 135°C and reacted for 4h, then heated to 280°C to distill the product, to obtain crude phosphate base oil A, the crude phosphate base oil A was mixed with a certain amount of activated carbon, magnesium silicate at 90°C and stirred for 1h, then filtered to obtain base oil A.

[0087] Preparation Example 2

[0088] To a three necked flask was added 711.42 parts of phenol and heated to 50°C. Then 17.2 parts of anhydrous aluminum chloride - calcium chloride dual catalyst was added. Then isobutylene was bubbled into the reaction mixture and stirred vigorously until 169 parts of isobutylene was absorbed. The reaction mixture was then cooled to 15°C and 386.4 parts of phosphorous oxychloride was added over a period of 40 minutes while maintaining the reaction mixture at 50°C. The resulting mixture was then heated gradually to 150°C over a period of 4 hours and maintained at 150°C for another 4 hours. The temperature was then raised to 210°C and maintained for 2 hours.

[0089] The resulting product was then cooled and washed with a mixture of 110 parts of concentrated hydrochloric acid and 2200 parts of water at 60°C for 30 minutes. Then it was washed with a mixture of 55 parts of concentrated hydrochloric acid and 2200 parts of water at 60°C for 10 minutes. Then it was washed with 2200 parts of distilled water at 60°C for 10 minutes. The product was then distilled to remove the toluene and the fraction distilled at a boiling point of 219°C to 260°C was collected. The fraction was first washed with a mixture of 34.5 parts of 40% sodium hydroxide solution and 1340 parts of water at 40°C for 2.5 hours and then with 17.25 parts of 40% sodium hydroxide solution and 1340 parts of water at 40°C for 1 hour. After the base wash, the product was washed with 2200 parts of water at 40°C for four times, each for 30 minutes to remove the sodium hydroxide. The product was then dehydrated at 95°C and -0.098 MPa for 1 hour to obtain crude phosphate ester base oil B. The crude phosphate ester base oil B was mixed with a certain amount of activated carbon and magnesium silicate at 90°C for 1 hour and then filtered to obtain base oil B.

[0090] Preparation Example 3

[0091] To a three necked flask was added 803 parts of a mixture of triphenyl phosphate and p-tert-butyl phenol and 8 parts of anhydrous potassium carbonate. The mixture was then subjected to transesterification under vacuum at -0.002 MPa. The temperature in the three necked flask was then raised from 130°C to 220°C and most of the 4-tert-butyl phenol was removed. The temperature was then raised to 250°C to completely remove the remaining tert-butyl phenol and maintained at 220°C for 20 minutes. After the distillation was completed, the reaction mixture was cooled to 45°C and neutralized with hydrochloric acid. The mixture was stirred for 3.5 hours and the precipitate was filtered off. The fraction having a boiling point of 260°C to 300°C was collected under vacuum at -0.002 MPa to obtain crude phosphate ester base oil B. The crude phosphate ester base oil B was mixed with a certain amount of activated carbon and magnesium silicate at 90°C for 1 hour and then filtered to obtain base oil B.

[0092] Example 1

[0093] This example is used to illustrate the preparation of the fire-retardant hydraulic oil by the method described in the present application, which comprises: mixing 98.951 g of base oil A (the properties and composition of the base oil are shown in Table 1), 0.5 g of antioxidant (0.02 g of 2,2,4-trimethyl-1,2-dihydroquinoline dimer and 0.03 g of octyl butyl diphenylamine and 0.3 g of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and 0.15 g of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol)), 0.008 g of copper corrosion inhibitor (0.006 g of methylbenzotriazole and 0.002 g of N,N-di(2-ethylhexyl)-1H-methylbenzotriazole-1-methylamine), 0.008 g of rust inhibitor (0.002 g of dodecenyl succinic acid methyl ester and 0.006 g of oleoyl sarcosine), 0.003 g of antifoaming agent (a mixture prepared according to the mass ratio of polydimethylsiloxane:trifluoropropyl silicone oil:polyacrylate:polydiethylsiloxane being 0.4:0.02:0.02:0.7, wherein the kinematic viscosity of the polydimethylsiloxane at 25°C is 350 mm 2 / s, the kinematic viscosity of the trifluoropropyl silicone oil at 25°C is 9320 mm 2 / s, the kinematic viscosity of the polyacrylate at 25°C is 152 mm 2 / s, the kinematic viscosity of the polydiethylsiloxane at 200°C is 3.2 mm 2 / s), 0.03 g of demulsifier (prepared according to the mass ratio of polyoxyethylene polyoxypropylene polyether:diamine propylene oxide polymer being 0.5:0.5), and 0.5 g of hydrolysis inhibitor (prepared according to the mass ratio of neopentyl glycol diglycidyl ether:butyl epoxy soyate:oxazoline derivative:N,N'-di(2,6-diisopropylphenyl)carbodiimide:triethanolamine:alkyl diphenylamine being 0.9:2:0.1:1:0.01:0.09) are mixed and stirred uniformly, and then dehydrated at 95°C and -0.098 MPa for 1.5 h to prepare hydraulic oil A1.

[0094] Example 2

[0095] This example is used to illustrate the preparation of the fire-retardant hydraulic oil by the method described in the present application, which comprises mixing 94.79 g of base oil A (the properties and composition of the base oil are shown in Table 1), 3 g of antioxidant (0.12 g of 2,2,4-trimethyl-1,2-dihydroquinoline dimer and 0.18 g of octylbutyl diphenylamine and 1.8 g of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and 0.9 g of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol)), 0.03 g of copper corrosion inhibitor (0.023 g of methylbenzotriazole and 0.007 g of N,N-di(2-ethylhexyl)-1H-methylbenzotriazole-1-methanamine), 0.03 g of rust inhibitor (0.023 g of dodecenyl succinic acid methyl ester and 0.007 g of oleoyl sarcosine), 0.05 g of antifoaming agent (a mixture prepared according to the mass ratio of polydimethylsiloxane:trifluoropropyl silicone oil:polyacrylate:polydiethylsiloxane of 0.4:0.02:0.02:0.7, wherein the kinematic viscosity of the polydimethylsiloxane at 25°C is 350 mm 2 / s, the kinematic viscosity of the trifluoropropyl silicone oil at 25°C is 9320 mm 2 / s, the kinematic viscosity of the polyacrylate at 25°C is 152 mm 2 / s, and the kinematic viscosity of the polydiethylsiloxane at 200°C is 3.2 mm 2 / s), 0.1 g of demulsifier (prepared according to the mass ratio of polyoxyethylene polyoxypropylene polyether:diamine propylene oxide polymer of 0.5:0.5), and 2 g of hydrolysis inhibitor (prepared according to the mass ratio of neopentyl glycol diglycidyl ether:butyl epoxy soyate:oxazoline derivative:N,N'-di(2,6-diisopropylphenyl)carbodiimide:triethanolamine:alkyl diphenylamine of 0.9:2:0.1:1:0.01:0.09) are mixed and stirred uniformly, and dehydrated at 95°C and -0.098 MPa for 1.5 h to prepare hydraulic oil A2.

[0096] Example 3

[0097] This example is used to illustrate the preparation of a fire-retardant hydraulic oil by the method described in the present application, which comprises: mixing 98.31 g of base oil A (the properties and composition of the base oil are shown in Table 1), 1 g of antioxidant (0.04 g of 2,2,4-trimethyl-1,2-dihydroquinoline dimer and 0.06 g of octyl butyl diphenylamine and 0.6 g of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and 0.3 g of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol)), 0.01 g of copper corrosion inhibitor (0.008 g of methylbenzotriazole and 0.002 g of N,N-di(2-ethylhexyl)-1H-methylbenzotriazole-1-methylamine), 0.01 g of rust inhibitor (0.008 g of dodecenyl succinic acid methyl ester and 0.002 g of oleoyl sarcosine), 0.01 g of antifoaming agent (a mixture prepared according to a mass ratio of polydimethylsiloxane:trifluoropropyl silicone oil:polyacrylate:polydiethylsiloxane of 0.4:0.02:0.02:0.7, wherein the kinematic viscosity of the polydimethylsiloxane at 25°C is 350 mm 2 / s, the kinematic viscosity of the trifluoropropyl silicone oil at 25°C is 9320 mm 2 / s, the kinematic viscosity of the polyacrylate at 25°C is 152 mm 2 / s, and the kinematic viscosity of the polydiethylsiloxane at 200°C is 3.2 mm 2 / s), 0.06 g of demulsifier (prepared according to a mass ratio of polyoxyethylene polyoxypropylene polyether:diamine propylene oxide polymer of 0.5:0.5), and 0.6 g of hydrolysis inhibitor (prepared according to a mass ratio of neopentyl glycol diglycidyl ether:butyl epoxy soyate:oxazoline derivative:N,N'-di(2,6-diisopropylphenyl)carbodiimide:triethanolamine:alkyl diphenylamine of 0.9:2:0.1:1:0.01:0.09) are mixed and stirred uniformly, and dehydrated at 95°C and -0.098 MPa for 1.5 h to prepare hydraulic oil A3.

[0098] Example 4

[0099] The method of Example 1 is followed, except that base oil A is replaced by base oil B (the properties and composition of the base oil are shown in Table 2) to prepare hydraulic oil A4.

[0100] Example 5

[0101] The method of Example 1 is followed, except that base oil A is replaced by base oil C (the properties and composition of the base oil are shown in Table 3) to prepare hydraulic oil A5.

[0102] Example 6

[0103] Hydraulic oil A6 was prepared according to the method of Example 1, except that the base oil was a mixture of base oil A and base oil B.

[0104] Example 7

[0105] Hydraulic oil A7 was prepared according to the method of Example 1, except that the base oil was a mixture of base oil A, base oil B and base oil C.

[0106] Example 8

[0107] Hydraulic oil A8 was prepared according to the method of Example 1, except that the antioxidant was a mixture of 0.2 g of 4,6-bis(octylthiomethyl) o-cresol and 0.3 g of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene.

[0108] Example 9

[0109] Hydraulic oil A9 was prepared according to the method of Example 1, except that the copper corrosion inhibitor was a mixture of 0.004 g of N,N'-bis(salicylidene)-1,2- propanediamine and 0.004 g of 1,3,4-thiadiazole-2,5-dithiobutyrate.

[0110] Example 10

[0111] Hydraulic oil A10 was prepared according to the method of Example 1, except that the rust inhibitor was 0.008 g of imidazoline alcohol.

[0112] Example 11

[0113] Hydraulic oil A11 was prepared according to the method of Example 1, except that the antifoam agent was 0.003 g of polyacrylate.

[0114] Example 12

[0115] Hydraulic oil A12 was prepared according to the method of Example 1, except that the demulsifier was 0.03 g of diamine propylene oxide polymer.

[0116] Example 13

[0117] Hydraulic oil A13 was prepared according to the method of Example 1, except that the hydrolysis inhibitor was 0.5 g of triethanolamine.

[0118] Example 14

[0119] Hydraulic oil A14 was prepared according to the method of Example 1, except that the hydraulic oil was 100 g of base oil.

[0120] Comparative Example 1

[0121] Hydraulic oil B1 was prepared according to the method of Example 1, except that the hydraulic oil did not contain the anti-hydrolysis agent.

[0122] Comparative Example 2

[0123] Hydraulic oil B2 was prepared according to the method of Example 1, except that the base oil was replaced by t-butyl phenyl phosphate with a kinematic viscosity of 100 mm 2 at 40°C.

[0124] Test Example

[0125] The properties of the hydraulic oils prepared in each of Examples 1-14 and Comparative Examples 1-2 were tested, and the test results are shown in Table 5.

[0126] Oxidation life was measured by the method of ASTM D 943, and the instrument model was TS-1.

[0127] Anti-hydrolysis performance was measured by the method of NB / SH / T 0301, and the instrument model was TSY-1220.

[0128] Anti-foaming performance was measured by the method of GB / T 12579, and the instrument model was BF-24.

[0129] Anti-corrosion performance was measured by the method of GB / T 5096, and the instrument model was ST5096-1A.

[0130] Anti-emulsification performance was measured by the method of GB / T 7305, and the instrument model was BF-25A.

[0131] The test method for anti-accelerated aging performance was as follows: 500 g of the test sample was loaded into a 500 mL thick borosilicate glass with a silk mouth bottle, and catalytic copper wire coil, steel sheet, deionized water, and catalytic materials (the amount and specifications of the test materials are shown in Table 4) for accelerating oil quality deterioration such as deteriorated phosphate ester anti-flame oil were added, and then the opening was placed in a 120±2°C oven. When the acid value reached 0.2 mgKOH / g, the test was stopped, and the time required for the acid value to reach 0.2 was recorded. The longer the time, the better the anti-accelerated aging performance.

[0132] Table 1 Properties and composition of base oil A

[0133]

[0134] Note: * is the composition and content of the hydrolysis product of mixture A, which indicates the composition of mixture A.

[0135] ** including 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 3,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2,4,5-trimethylphenol six isomers.

[0136] Table 2 Properties and compositions of base oil B

[0137]

[0138]

[0139] Table 3 Properties and compositions of base oil C

[0140]

[0141] Table 4 Test material quantity and specifications required for accelerated aging test

[0142]

[0143]

[0144] Table 5

[0145]

[0146] Table 5 (continued)

[0147]

[0148]

[0149] Table 5 (continued)

[0150]

[0151] As can be seen from the results in Table 5, the fire-retardant hydraulic oils A1-A14 prepared in Examples 1-14 using the base oil and additives provided by the present application have longer oxidation life, more excellent hydrolysis stability, foam property, anti-emulsification property, anti-copper corrosion property and anti-accelerated aging property than the hydraulic oil B2 prepared in Comparative Example 2, effectively slow down the deterioration rate of the fire-retardant hydraulic oil, prolong the service life, and ensure the reliability of operation of large steam turbine units of thermal power and nuclear power.

[0152] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A flame-retardant hydraulic oil, characterized in that, The hydraulic oil is composed of base oil, antioxidant, copper corrosion inhibitor, rust inhibitor, antifoaming agent, demulsifier and anti-hydrolysis agent; wherein the base oil is selected from at least one of mixture A, mixture B and mixture C; The preparation method of the mixture A includes: 3-Methylphenol, trimethylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 3-ethylphenol, and 4-ethylphenol were mixed, and aluminum chloride catalyst was added and stirred. When the temperature dropped to 50°C, phosphorus oxychloride was added, the temperature was raised to 135°C and reacted for 4 hours. Then the temperature was raised to 280°C and the product was distilled off. The product was mixed with activated carbon and magnesium silicate and filtered to obtain mixture A. In the mixture B, the mass ratio of (4-tert-butylphenyl)diphenyl phosphate, di(4-tert-butylphenyl)phenyl phosphate, tri(4-tert-butylphenyl) phosphate and triphenyl phosphate is (74-84):(16-24):(0.1-1):(0.1-1). In the mixture C, the mass ratio of (4-tert-butylphenyl)diphenyl phosphate, di(4-tert-butylphenyl)phenyl phosphate, tri(4-tert-butylphenyl) phosphate, and triphenyl phosphate is (76-81):(16-20):(0.2-3):(0.2-3). The base oil has a kinematic viscosity of ≥23 mm at 50°C. 2 / s, and not exceeding 33 mm 2 / s; Based on the total mass of the hydraulic oil, the content of the base oil is 91.5-99.35 wt%; the content of the antioxidant is 0.53-3 wt%; the content of the copper corrosion inhibitor is 0.005-1 wt%; the content of the rust inhibitor is 0.005-0.2 wt%; the content of the antifoaming agent is 0.005-0.1 wt%; the content of the demulsifier is 0.005-0.2 wt%; and the content of the anti-hydrolysis agent is 0.1-4 wt%. The anti-hydrolysis agent is a mixture of neopentyl glycol diglycidyl ether, epoxidized soybean oleate butyl ester, oxazoline derivative, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, triethanolamine, and alkyl diphenylamine. The mass ratio of neopentyl glycol diglycidyl ether, epoxidized soybean oleate butyl ester, oxazoline derivative, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, triethanolamine, and alkyl diphenylamine in the anti-hydrolysis agent is (0.2-5):(0.05-5):(0.005-2):(0.005-3):(0.005-1):(0.05-4). The antioxidant is selected from at least one of 2,2,4-trimethyl-1,2-dihydroquinoline dimer, octylbutyldiphenylamine, 4,6-di(octylthiomethyl)o-cresol, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and 2,2'-methylenebis-(4-methyl-6-tert-butylphenol); The copper corrosion inhibitor is selected from at least one of N,N'-bis(salicylyl)-1,2-propanediamine, 2-mercaptobenzothiazole, benzotriazole, methylbenzotriazole, carboxybenzotriazole, N,N-di(2-ethylhexyl)-1H-methylbenzotriazole-1-methylamine, 1,3,4-thiadiazole-2,5-dithiododecyl ester and 1,3,4-thiadiazole-2,5-dithiohexadecyl ester; The rust inhibitor is selected from at least one of 1-aminoethyl-2-(heptadecenyl)imidazoline dodecenyl succinate, methyl dodecenyl succinate, oleoyl sarcosine, oleoyl amino alkylamine, and imidazoline alcohol; The antifoaming agent is selected from at least one of polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate, and polydiethylsiloxane; The demulsifier is a polymer of polyoxyethylene polyoxypropylene polyether and diamine epoxy propylene oxide; The base oil has a dimethylphenol residue of ≤0.1wt%, an acid value of ≤0.03mgKOH / g, a water-soluble acid pH of 5.6-8, and a density of 1.13-1.17g / cm³ at 20℃. 3 Autoignition point ≥ 530℃, air release value at 50℃ ≤ 4min, flash point ≥ 245℃, foaming characteristics at 24℃ ≤ 10mL / 0mL, resistivity at 20℃ ≥ 2×10 10 Ω·cm.

2. The hydraulic oil according to claim 1, wherein, Based on the total mass of the hydraulic oil, the content of the copper corrosion inhibitor is 0.008-0.03 wt%; the content of the rust inhibitor is 0.008-0.03 wt%; the content of the antifoaming agent is 0.005-0.05 wt%; the content of the demulsifier is 0.03-0.1 wt%; the content of the anti-hydrolysis agent is 0.5-2 wt%, and the sum of the contents of all components in the hydraulic oil is 100 wt%.

3. The hydraulic oil according to claim 1 or 2, wherein, The antifoaming agent is a mixture of polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane.

4. The hydraulic oil according to claim 3, wherein, The kinematic viscosity of the polydimethylsiloxane at 25°C is 350-1000 mm. 2 / s; And / or, the kinematic viscosity of the trifluoropropyl silicone oil at 25°C is 8000-10000 mm³. 2 / s; And / or, the kinematic viscosity of the polyacrylate at 25°C is 90-180 mmHg. 2 / s; And / or, the kinematic viscosity of the polydiethylsiloxane at 200°C is 2.8-4.8 mm. 2 / s.

5. The hydraulic oil according to claim 4, wherein, In the antifoaming agent, the mass ratio of polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane is (0.1-0.6):(0.01-0.1):(0.01-0.1):(0.5-0.9).

6. The hydraulic oil according to claim 5, wherein, In the antifoaming agent, the mass ratio of polydimethylsiloxane, trifluoropropyl silicone oil, polyacrylate and polydiethylsiloxane is (0.3-0.5):(0.01-0.03):(0.01-0.03):(0.6-0.9).

7. The hydraulic oil according to claim 1, wherein, The kinematic viscosity of the polyoxyethylene polyoxypropylene polyether at 100°C is 10-16 mm. 2 / s; And / or, the kinematic viscosity of the diamine propylene oxide polymer at 100°C is 14-23 mm. 2 / s.

8. The hydraulic oil according to claim 7, wherein, The mass ratio of the polyoxyethylene polyoxypropylene polyether to the diamine epoxy propylene polymer is (0.5-0.7):(0.1-0.6).

9. A method for preparing the flame-retardant hydraulic oil according to any one of claims 1-8, characterized in that, The method includes mixing base oil, antioxidant, copper corrosion inhibitor, rust inhibitor, antifoaming agent, antihydrolysis agent and demulsifier.

10. The preparation method according to claim 9, wherein, The mixing conditions include: a temperature of 80-100℃, a pressure of -0.099MPa to -0.096MPa, and a time of 1-2h.

11. The application of the hydraulic oil according to any one of claims 1-8 or the flame-retardant hydraulic oil prepared by the preparation method according to any one of claims 9-10 in a steam turbine.

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