A rust-preventive coal mine hydraulic support concentrate and a method for preparing the same

Abstract

The present application provides a kind of anti-rust coal mine hydraulic support concentrate, by weight percentage, including: polyalkylene glycol: 4.0~10.0%;Wetting agent: 15.0~35.0%;Surfactant: 2.0~4.0%;Molybdenum dialkyldithiophosphate: 1.0~3.0%;Polytribasic acid: 1.5~4.5%;Ethylene diamine phosphate: 2.0~4.0%;Urea: 3.0~10.0%;Phytic acid triethanolamine: 1.0~3.0%;Sodium mercaptobenzothiazole: 0.5~1.5%;Modified sheet TiO2: 2.1~3.4%;Water-soluble fluorescent green: 50~200ppm;Deionized water: the balance.The anti-rust hydraulic support concentrate of the present application, cast iron piece anti-rust test and No.15 steel bar corrosion test all pass 48 hours, increase 1 times of the margin compared with standard requirement, lubricity (PB value) is 804N, increase 2.05 times compared with standard, can effectively solve the rust of key parts of equipment, ensure the safe operation of hydraulic support equipment, effectively prolong service life.

Description

Technical Field

[0001] This invention relates to the field of lubricating oil, and more specifically to a rust-preventive hydraulic support concentrate for coal mines and its preparation method. Background Technology

[0002] Hydraulic supports are key equipment in coal mining, and the transmission medium of hydraulic supports is the "blood" of the hydraulic support system, providing transmission and protection. Its performance directly affects coal mining safety and efficiency. In recent years, my country's mechanized coal mining technology (fully mechanized and high-grade conventional mining) has developed rapidly, with hydraulic supports and single-prop supports being the main support methods. These hydraulic transmission systems consume a large amount of transmission medium annually. Simultaneously, with the continuous improvement of coal mining mechanization, the demand for support concentrate, as a transmission medium, is increasing. The working medium for hydraulic supports includes hydraulic support emulsion oil and hydraulic support concentrate. After dilution with water, it serves as a pressure transmission medium, requiring certain levels of lubricity, rust prevention, dispersibility, and biological stability. Emulsion oil, composed of mineral oil and surfactants, has the advantage of good lubricity but disadvantages such as short lifespan and potential environmental pollution. Concentrates are synthetic products without mineral oil, offering good dispersibility, long lifespan, and less environmental impact. A common disadvantage is their poor rust prevention, which can easily cause equipment and pipeline corrosion, shorten equipment overhaul intervals, and even lead to pressure transmission failure and accidents. Summary of the Invention

[0003] The technical problem to be solved: The purpose of this invention is to provide a rust-proof coal mine hydraulic support concentrate, which is obtained by compounding surfactants, silane coupling agents and flaky TiO2 particles to obtain a coal mine hydraulic support concentrate with rust-proof function.

[0004] Technical solution: A rust-proof hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0005] Polyalkylene glycol: 4.0–10.0%

[0006] Wetting agent: 15.0%–35.0%

[0007] Surfactant: 2.0–4.0%

[0008] Dialkyl dithiophosphate molybdenum: 1.0–3.0%

[0009] Polytercarboxylic acid: 1.5–4.5%

[0010] Ethylenediamine phosphate: 2.0–4.0%

[0011] Urea: 3.0–10.0%

[0012] Triethanolamine phytate: 1.0–3.0%

[0013] Sodium mercaptobenzothiazole: 0.5–1.5%

[0014] Modified flaky TiO2: 2.1–3.4%

[0015] Water-soluble fluorescent green: 50–200 ppm

[0016] Deionized water: Balance.

[0017] Preferably, the wetting agent is any one or a mixture of two or more of triglycerides, glycerol, or propylene glycol. Preferably, the surfactant is any one of sebacic acid diethanolamide, oleic acid diethanolamide, or borate diethanolamide.

[0018] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0019] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to hydrochloric acid with a concentration of 34-38% and stirred vigorously. After stirring for 10-20 min, a mixture of ethanol and P123 triblock copolymer was added. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor to obtain a precipitate. The precipitate was annealed in a muffle furnace to obtain flake-shaped TiO2 particles.

[0020] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate are mixed and reacted in an oil bath under nitrogen protection to obtain composite coupling agent.

[0021] S13. Preparation of modified flake TiO2: Flake TiO2 particles are dissolved in an ethanol / water solution with a volume ratio of 3:1, ultrasonically dispersed for 10-20 min, and then the composite coupling agent prepared in step S2 is added. The mixture is refluxed at 60-70℃ for 15-30 h to obtain modified flake TiO2. Preferably, the mass ratio of the titanium isopropoxide, hydrochloric acid, ethanol, and P123 triblock copolymer is 10:0.5-1:25-30:1.8-2.3. Preferably, the hydrothermal reaction temperature is 170-185℃ for 10-30 h, and the annealing temperature is 500-550℃ for 2-5 h.

[0022] Preferably, the mass ratio of Tween 20, propyltrimethoxysilane isocyanate, and dibutyltin dilaurate is 12.2-12.8:1.8-2.0:0.3, the oil bath reaction temperature is 40-60℃, and the time is 15-30h.

[0023] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0024] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0025] S2. Add water to the above mixture, heat to 100-120℃, stir for 30-40 min, and then ultrasonically disperse for 30-40 min; S3. Add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytercarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green to the above mixed solution in sequence, maintain the temperature at 50-60℃, stir for 30-50 min, and obtain a rust-proof coal mine hydraulic support concentrate.

[0026] Beneficial effects: The rust-proof coal mine hydraulic support concentrate prepared by this invention has the following advantages:

[0027] 1. This invention uses Tween 20, which has many polar groups, to graft onto flake-shaped TiO2 particles via a silane coupling agent, resulting in long molecular chains with polar groups on the surface. Because the modified flake-shaped TiO2 has long molecular chains and many polar groups, the molecular chains can be adsorbed and accumulated on the metal surface to form a thicker protective film. Furthermore, since TiO2 is flake-shaped, when the metal surface is rubbed, the flake-shaped TiO2 can embed into the defects on the metal surface, forming a protective ceramic film and improving the corrosion resistance of the metal.

[0028] 2. The rust-proof hydraulic support concentrate of the present invention passed the rust prevention test of cast iron sheet and the corrosion test of No. 15 steel bar for 48 hours, which is twice the standard requirement. The lubricity (PB value) is 804N, which is 2.05 times higher than the standard. It can effectively solve the corrosion of key parts of the equipment, ensure the safe operation of hydraulic support equipment, and effectively extend the service life. Detailed Implementation

[0029] The present invention will be further described below with reference to embodiments. These embodiments are illustrative of the present invention, but the present invention is not limited to these embodiments:

[0030] Example 1

[0031] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0032] Polyalkylene glycol: 4.0%

[0033] Wetting agent - triglycerides: 35.0%

[0034] Surfactant - Sebacic acid diethanolamide: 4.0%

[0035] Dialkyl dithiophosphate molybdenum: 3.0%

[0036] Polytercarboxylic acid: 4.5%

[0037] Ethylenediamine phosphate: 4.0%

[0038] Urea: 3.0%

[0039] Triethanolamine phytate: 1.0%

[0040] Sodium mercaptobenzothiazole: 0.5%

[0041] Modified flaky TiO2: 2.1%

[0042] Water-soluble fluorescent green: 50 ppm

[0043] Deionized water: Balance;

[0044] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0045] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0046] S2. Add water to the above mixture, heat to 100°C, stir for 30 minutes, and then ultrasonically disperse for 30 minutes;

[0047] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 60°C, stir for 30 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0048] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0049] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 34% hydrochloric acid under vigorous stirring. After stirring for 20 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:0.5:25:1.8. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 170℃ for 10 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 500℃ for 2 h to obtain flake-shaped TiO2 particles.

[0050] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate were mixed in a mass ratio of 12.2:1.8:0.3 and reacted in an oil bath under nitrogen protection at a temperature of 40°C for 30 hours to obtain the composite coupling agent.

[0051] S13. Preparation of modified sheet-like TiO2: The sheet-like TiO2 particles were dissolved in an ethanol / water solution with a volume ratio of 3:1, ultrasonically dispersed for 10 min, and then the composite coupling agent prepared in step S2 was added. The mixture was refluxed at 60℃ for 30 h to obtain modified sheet-like TiO2.

[0052] Example 2

[0053] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0054] Polyalkylene glycol: 10.0%

[0055] Wetting agent - triglycerides, glycerin, or propylene glycol: 15.0%

[0056] Surfactant - sebacic acid diethanolamide, oleic acid diethanolamide, or borate diethanolamide: 2.0%

[0057] Dialkyl dithiophosphate molybdenum: 1.0%

[0058] Polytercarboxylic acid: 1.5%

[0059] Ethylenediamine phosphate: 2.0%

[0060] Urea: 10.0%

[0061] Phytate triethanolamine: 3.0%

[0062] Sodium mercaptobenzothiazole: 1.5%

[0063] Modified flaky TiO2: 3.4%

[0064] Water-soluble fluorescent green: 200 ppm

[0065] Deionized water: Balance;

[0066] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0067] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0068] S2. Add water to the above mixture, heat to 120°C, stir for 40 minutes, and then ultrasonically disperse for 40 minutes;

[0069] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 50°C, stir for 50 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0070] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0071] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 38% hydrochloric acid under vigorous stirring. After stirring for 10 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:1:30:2.3. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 185℃ for 30 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 550℃ for 5 h to obtain flake-shaped TiO2 particles.

[0072] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate were mixed in a mass ratio of 12.8:2.0:0.3 and reacted in an oil bath under nitrogen protection. The oil bath reaction temperature was 60℃ and the time was 15h to obtain the composite coupling agent.

[0073] S13. Preparation of modified sheet TiO2: Dissolve sheet TiO2 particles in an ethanol / water solution with a volume ratio of 3:1, disperse ultrasonically for 20 min, add the composite coupling agent prepared in step S2, and reflux at 70℃ for 15 h to obtain modified sheet TiO2.

[0074] Example 3

[0075] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0076] Polyalkylene glycol: 6.0%

[0077] Wetting agent - propylene glycol: 20.0%

[0078] Surfactant - Borate diethanolamide: 2.5%

[0079] Dialkyl dithiophosphate molybdenum: 1.5%

[0080] Polytercarboxylic acid: 2.5%

[0081] Ethylenediamine phosphate: 3.5%

[0082] Urea: 5.0%

[0083] Triethanolamine phytate: 2.5%

[0084] Sodium mercaptobenzothiazole: 0.8%

[0085] Modified flaky TiO2: 2.5%

[0086] Water-soluble fluorescent green: 100 ppm

[0087] Deionized water: Balance;

[0088] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0089] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0090] S2. Add water to the above mixture, heat to 105°C, stir for 30 minutes, and then ultrasonically disperse for 40 minutes;

[0091] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 50°C, stir for 35 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0092] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0093] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 38% hydrochloric acid under vigorous stirring. After stirring for 15 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:0.6:25:2. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 175℃ for 25 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 520℃ for 4 h to obtain flake-shaped TiO2 particles.

[0094] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate were mixed in a mass ratio of 12.6:2.0:0.3 and reacted in an oil bath under nitrogen protection at a temperature of 45°C for 28 hours to obtain the composite coupling agent.

[0095] S13. Preparation of modified flake TiO2: Flake TiO2 particles were dissolved in an ethanol / water solution with a volume ratio of 3:1, ultrasonically dispersed for 20 min, and then the composite coupling agent prepared in step S2 was added. The mixture was refluxed at 60 °C for 26 h to obtain modified flake TiO2.

[0096] Example 4

[0097] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0098] Polyalkylene glycol: 8.0%

[0099] Wetting agent - Glycerin: 30.0%

[0100] Surfactant - Oleic acid diethanolamide: 3.5%

[0101] Dialkyl dithiophosphate molybdenum: 2.5%

[0102] Polytercarboxylic acid: 3.5%

[0103] Ethylenediamine phosphate: 2.5%

[0104] Urea: 7.0%

[0105] Phytate triethanolamine: 1.5%

[0106] Sodium mercaptobenzothiazole: 1.2%

[0107] Modified flaky TiO2: 3.0%

[0108] Water-soluble fluorescent green: 160 ppm

[0109] Deionized water: Balance;

[0110] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0111] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0112] S2. Add water to the above mixture, heat to 115°C, stir for 40 minutes, and then ultrasonically disperse for 30 minutes;

[0113] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 60°C, stir for 45 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0114] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0115] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 36% hydrochloric acid under vigorous stirring. After stirring for 16 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:0.8:23:2.2. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 180℃ for 15 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 550℃ for 3 h to obtain flake-shaped TiO2 particles.

[0116] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate were mixed in a mass ratio of 12.6:2.0:0.3 and reacted in an oil bath under nitrogen protection. The oil bath reaction temperature was 55℃ and the time was 20h to obtain the composite coupling agent.

[0117] S13. Preparation of modified sheet TiO2: Dissolve sheet TiO2 particles in an ethanol / water solution with a volume ratio of 3:1, disperse by ultrasonication for 10 min, add the composite coupling agent prepared in step S2, and reflux at 70℃ for 18 h to obtain modified sheet TiO2.

[0118] Example 5

[0119] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0120] Polyalkylene glycol: 7.0%

[0121] Wetting agent - Glycerin: 25.0%

[0122] Surfactant - Oleic acid diethanolamide: 3.0%

[0123] Dialkyl dithiophosphate molybdenum: 2.0%

[0124] Polytercarboxylic acid: 3.0%

[0125] Ethylenediamine phosphate: 3.0%

[0126] Urea: 6.0%

[0127] Triethanolamine phytate: 2.0%

[0128] Sodium mercaptobenzothiazole: 1.0%

[0129] Modified flaky TiO2: 2.8%

[0130] Water-soluble fluorescent green: 140 ppm

[0131] Deionized water: Balance;

[0132] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0133] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0134] S2. Add water to the above mixture, heat to 110°C, stir for 35 minutes, and then ultrasonically disperse for 35 minutes;

[0135] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 55℃, stir for 40 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0136] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0137] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 36% hydrochloric acid under vigorous stirring. After stirring for 15 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:0.7:28:2.1. After stirring, ethylene glycol was added and stirring continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 178℃ for 20 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 540℃ for 3.6 h to obtain flake-shaped TiO2 particles.

[0138] S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate were mixed in a mass ratio of 12.5:1.9:0.3 and reacted in an oil bath under nitrogen protection. The oil bath reaction temperature was 50℃ and the time was 25h to obtain the composite coupling agent.

[0139] S13. Preparation of modified sheet TiO2: The sheet TiO2 particles were dissolved in an ethanol / water solution with a volume ratio of 3:1, ultrasonically dispersed for 15 min, and then the composite coupling agent prepared in step S2 was added. The mixture was refluxed at 65℃ for 22 h to obtain modified sheet TiO2.

[0140] Comparative Example 1

[0141] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0142] Polyalkylene glycol: 7.0%

[0143] Wetting agent - Glycerin: 25.0%

[0144] Surfactant - Oleic acid diethanolamide: 3.0%

[0145] Dialkyl dithiophosphate molybdenum: 2.0%

[0146] Polytercarboxylic acid: 3.0%

[0147] Ethylenediamine phosphate: 3.0%

[0148] Urea: 6.0%

[0149] Triethanolamine phytate: 2.0%

[0150] Sodium mercaptobenzothiazole: 1.0%

[0151] Modified flaky TiO2: 2.8%

[0152] Water-soluble fluorescent green: 140 ppm

[0153] Deionized water: Balance;

[0154] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0155] S1. Mix the surfactant and wetting agent, then modify the flake TiO2 and mix thoroughly;

[0156] S2. Add water to the above mixture, heat to 110°C, stir for 35 minutes, and then ultrasonically disperse for 35 minutes;

[0157] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 55℃, stir for 40 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0158] Preferably, the method for preparing the modified sheet-like TiO2 is as follows:

[0159] S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to 36% hydrochloric acid under vigorous stirring. After stirring for 15 min, a mixture of ethanol and P123 triblock copolymer was added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer was 10:0.7:28:2.1. After stirring, ethylene glycol was added and stirring continued. The mixture was then reacted in a hydrothermal reactor at a temperature of 178℃ for 20 h to obtain a precipitate. The precipitate was then annealed in a muffle furnace at a temperature of 540℃ for 3.6 h to obtain flake-shaped TiO2 particles.

[0160] S12. Preparation of modified flake TiO2: Flake TiO2 particles were dissolved in an ethanol / water solution with a volume ratio of 3:1 and ultrasonically dispersed for 15 min to obtain modified flake TiO2.

[0161] Comparative Example 2

[0162] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0163] Polyalkylene glycol: 6.0%

[0164] Wetting agent - propylene glycol: 20.0%

[0165] Surfactant - Borate diethanolamide: 2.5%

[0166] Dialkyl dithiophosphate molybdenum: 1.5%

[0167] Polytercarboxylic acid: 2.5%

[0168] Ethylenediamine phosphate: 3.5%

[0169] Urea: 5.0%

[0170] Triethanolamine phytate: 2.5%

[0171] Sodium mercaptobenzothiazole: 0.8%

[0172] Spherical nano-TiO2: 2.5%

[0173] Water-soluble fluorescent green: 100 ppm

[0174] Deionized water: Balance;

[0175] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0176] S1. Mix the surfactant and wetting agent, then mix with spherical nano-TiO2 until homogeneous;

[0177] S2. Add water to the above mixture, heat to 105°C, stir for 30 minutes, and then ultrasonically disperse for 40 minutes;

[0178] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 50°C, and stir for 35 min to obtain a rust-proof coal mine hydraulic support concentrate.

[0179] Comparative Example 3

[0180] A rust-resistant hydraulic support concentrate for coal mines, comprising, by weight percentage:

[0181] Polyalkylene glycol: 9.0%

[0182] Wetting agent - Glycerin: 32.0%

[0183] Surfactant - Oleic acid diethanolamide: 3.5%

[0184] Dialkyl dithiophosphate molybdenum: 2.5%

[0185] Polytercarboxylic acid: 3.2%

[0186] Ethylenediamine phosphate: 2.7%

[0187] Urea: 8.0%

[0188] Phytate triethanolamine: 1.5%

[0189] Sodium mercaptobenzothiazole: 1.2%

[0190] Flaky TiO2: 3.0%

[0191] Tween 20: 2.0%

[0192] Water-soluble fluorescent green: 160 ppm

[0193] Deionized water: Balance;

[0194] The above-mentioned method for preparing a rust-proof coal mine hydraulic support concentrate includes the following steps:

[0195] S1. Mix the surfactant, wetting agent and Tween 20, then mix the flake TiO2 evenly;

[0196] S2. Add water to the above mixture, heat to 115°C, stir for 40 minutes, and then ultrasonically disperse for 30 minutes;

[0197] S3. In the above mixed solution, add polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytricarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green in sequence, keep the temperature at 60°C, stir for 45 min, and obtain rust-proof coal mine hydraulic support concentrate.

[0198] Preferably, the preparation method of the sheet-like TiO2 is as follows: titanium isopropoxide is added to 36% hydrochloric acid under vigorous stirring. After stirring for 20 min, a mixture of ethanol and P123 triblock copolymer is added. The mass ratio of titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer is 10:0.8:23:2.2. After stirring, ethylene glycol is added and stirring is continued. The mixture is then reacted in a hydrothermal reactor at a temperature of 180°C for 15 h to obtain a precipitate. The precipitate is then annealed in a muffle furnace at a temperature of 550°C for 3 h to obtain sheet-like TiO2 particles.

[0199] The performance of the rust-proof coal mine hydraulic support concentrates prepared in the examples and comparative examples was tested:

[0200] Table 1 Reference Standard (MT 76-2002)

[0201] Rust prevention Corrosion resistant (No. 15 steel bar) Room temperature stability Example 1 No rust or discoloration after 48 hours No color change or corrosion after 48 hours Precipitates <0.1% Example 2 No rust or discoloration after 48 hours No color change or corrosion after 48 hours Precipitates <0.1% Example 3 No rust or discoloration after 48 hours No color change or corrosion after 48 hours Precipitates <0.1% Example 4 No rust or discoloration after 48 hours No color change or corrosion after 48 hours Precipitates <0.1% Example 5 No rust or discoloration after 48 hours No color change or corrosion after 48 hours Precipitates <0.1% Comparative Example 1 No rust or discoloration after 24 hours No color change or corrosion after 24 hours Precipitates <0.1% Comparative Example 2 No rust or discoloration after 24 hours No color change or corrosion after 30 hours Precipitates <0.1% Comparative Example 3 No rust or discoloration after 30 hours No color change or corrosion after 36 hours Precipitates <0.1%

[0202] Table 2 Reference Standard (GB / T 3142)

[0203]

[0204]

[0205] The hydraulic support concentrate prepared by this invention passed both the rust prevention test and the corrosion test of No. 15 steel bar after 48 hours, exceeding the standard requirement by 100%. Lubricity (P...) B The value is 804N, which is 2.05 times higher than the standard.

[0206] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A rust-proof hydraulic support concentrate for coal mines, characterized in that: By weight percentage, including: Polyalkylene glycol: 4.0–10.0% Wetting agent: 15.0%–35.0% Surfactant: 2.0–4.0% Dialkyl dithiophosphate molybdenum: 1.0–3.0% Polytercarboxylic acid: 1.5–4.5% Ethylenediamine phosphate: 2.0–4.0% Urea: 3.0–10.0% Triethanolamine phytate: 1.0–3.0% Sodium mercaptobenzothiazole: 0.5–1.5% Modified flaky TiO2: 2.1–3.4% Water-soluble fluorescent green: 50–200 ppm Deionized water: Balance; The method for preparing the modified sheet-like TiO2 is as follows: S11. Preparation of flake-shaped TiO2 particles: Titanium isopropoxide was added to hydrochloric acid with a concentration of 34-38% and stirred vigorously. After stirring for 10-20 min, a mixture of ethanol and P123 triblock copolymer was added. After stirring, ethylene glycol was added and stirring was continued. The mixture was then reacted in a hydrothermal reactor to obtain a precipitate. The precipitate was annealed in a muffle furnace to obtain flake-shaped TiO2 particles. S12. Preparation of composite coupling agent: Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate are mixed and reacted in an oil bath under nitrogen protection to obtain composite coupling agent; S13. Preparation of modified flake TiO2: Dissolve flake TiO2 particles in an ethanol / water solution with a volume ratio of 3:1, disperse ultrasonically for 10-20 min, add the composite coupling agent prepared in step S12, and reflux at 60-70℃ for 15-30 h to obtain modified flake TiO2.

2. The rust-proof coal mine hydraulic support concentrate according to claim 1, characterized in that: The wetting agent is any one or a mixture of two or more of triglycerides, glycerol, or propylene glycol.

3. The rust-proof hydraulic support concentrate for coal mines according to claim 1, characterized in that: The surfactant is any one of sebacic acid diethanolamide, oleic acid diethanolamide, or boric acid diethanolamide.

4. The rust-proof hydraulic support concentrate for coal mines according to claim 1, characterized in that: The mass ratio of the titanium isopropoxide, hydrochloric acid, ethanol and P123 triblock copolymer is 10:0.5-1:25-30:1.8-2.

3.

5. The rust-proof hydraulic support concentrate for coal mines according to claim 1, characterized in that: The reaction temperature in the hydrothermal reactor is 170-185℃ for 10-30 hours, and the annealing temperature is 500-550℃ for 2-5 hours.

6. The rust-proof hydraulic support concentrate for coal mines according to claim 1, characterized in that: The mass ratio of Tween 20, propyltrimethoxysilane isocyanate and dibutyltin dilaurate is 12.2-12.8:1.8-2.0:0.3, the oil bath reaction temperature is 40-60℃, and the time is 15-30h.

7. The method for preparing a rust-proof coal mine hydraulic support concentrate according to claim 1, characterized in that, Includes the following steps: S1. Mix the surfactant and wetting agent, then add the modified flake TiO2 and mix thoroughly; S2. Add water to the mixture obtained in S1, heat to 100-120℃, stir for 30-40 minutes, and then ultrasonically disperse for 30-40 minutes; S3. In the mixed solution obtained in S2, polyalkylene glycol, molybdenum dialkyl dithiophosphate, polytercarboxylic acid, ethylenediamine phosphate, urea, triethanolamine phytate, sodium mercaptobenzothiazole, and water-soluble fluorescent green are added sequentially. The temperature is maintained at 50-60℃ and the mixture is stirred for 30-50 minutes to obtain a rust-proof coal mine hydraulic support concentrate.

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