Formula and preparation method of emulsified oil concentrated solution for multifunctional hydraulic support

Abstract

The invention relates to the technical field of hydraulic transmission media, and discloses a formula and a preparation method of an emulsified oil concentrated solution for a multifunctional hydraulic support. Hexadecanedioic acid and N-(4-methoxyphenyl) ethylenediamine are used as raw materials, 2-bromoethane sodium sulfonate is used as a quaternization reagent, hydroxyl in the structure of the quaternization reagent and epoxy groups of epoxidized soybean oil are utilized to generate chemical bonding, and the emulsified oil concentrated solution for the multifunctional hydraulic support is prepared. The emulsified oil is compounded with organic alcohol amine, fatty acid and the like to obtain a formula of the emulsified oil concentrated solution for the multifunctional hydraulic support, which is good in dispersing performance, high in corrosion inhibition capability and high in extrusion wear resistance; the vegetable oil-based hard water-resistant corrosion inhibitor contains bicyclic imidazoline and quaternary ammonium salt structures, so that a compact physical and chemical adsorption film can be formed on the surface of metal; a sodium sulfonate group can be complexed with ions such as calcium and magnesium in hard water, so that the stability in the hard water is enhanced, and the hard water resistance is improved; the concentrated solution prepared by the invention is non-toxic and environment-friendly, and can meet the use of the hydraulic support under harsh working conditions.

Description

Technical Field

[0001] The invention relates to the technical field of hydraulic transmission media, in particular to a formula of an emulsified oil concentrate for a multifunctional hydraulic support and a preparation method thereof. Background Art

[0002] Hydraulic support is a very important mechanical equipment in coal mining work in the coal industry. Hydraulic support concentrate is the "blood" of the hydraulic support system and plays a transmission role. It directly affects the service life and safety of the equipment. If it is not selected properly, it will not only damage the equipment, but also cause safety accidents. The emulsified oil currently used in coal mines is a product synthesized based on 60-70% motor oil. It is called "emulsified oil", but the traditional hydraulic support fluid contains mineral oil, which is easy to precipitate oil and belongs to a thermodynamically unstable system. During use, there is still a certain amount of oil soap precipitation, causing the filter to be blocked. The filter needs to be cleaned frequently, and these precipitated oil soaps combine with coal dust to form a viscous substance that is difficult to clean, which will cause many troubles for on-site use. At the same time, the humid environment underground can easily cause corrosion to the hydraulic support, especially pitting corrosion, which seriously affects underground safety.

[0003] At present, the semi-synthetic hydraulic support concentrate widely used in the market has poor corrosion resistance and rust prevention performance of water-based products. The added inorganic corrosion inhibitors such as molybdate and sodium nitrite have certain corrosion inhibition effect, but sodium molybdate is expensive and sodium nitrite is carcinogenic. Conventional carboxylic acid organic corrosion inhibitors are cheap, but their overall corrosion inhibition performance is relatively weak, which limits their scope of use. Some people have proposed to use emulsified oil that can form O / W microemulsion to prepare hydraulic support emulsion to solve the problem of poor stability when preparing emulsion from mine water. However, from the actual use situation, the use of microemulsion as hydraulic support emulsion has better stability, but poor rust prevention performance; at the same time, it also does not solve the problem of high oil-based viscosity; in addition, the currently used concentrate still has the defect of polluting water resources. After the concentrate leaks and is discharged, it will continue to break the emulsion by itself in various complex situations, allowing the mineral oil to be released; therefore, it is also urgent to solve the problem of environmental pollution caused by emulsion.

[0004] Epoxidized soybean oil has single stability and biodegradability, making it one of the green base oils in the concentrate. The epoxy groups in its structure can react with hydroxyl groups to form a bond, and it has excellent lubrication and wear resistance. This application aims to develop a new type of synthetic hydraulic support concentrate based on vegetable oil as the base oil. Its comprehensive performance is not only superior to that of traditional emulsified oil, but also because the formula no longer contains mineral oil, it is environmentally friendly and has good corrosion resistance. The method is simple and novel, and has broad application prospects. Summary of the invention

[0005] The purpose of the present invention is to solve the problems of poor stability, high cost, lack of raw materials and low environmental performance of traditional emulsified oil used in hydraulic supports in the prior art, and to provide a formula of emulsified oil concentrate for multifunctional hydraulic supports and a preparation method thereof, which has good resistance to hard water, corrosion resistance and biodegradability, and can extend the service life of the equipment.

[0006] The present invention is achieved through the following technical solutions: The formula of the emulsified oil concentrate for the multifunctional hydraulic support is composed of the following raw materials in parts by weight: 12-18 parts of concentrate additives, 3-7 parts of vegetable oil-based hard water corrosion inhibitors and 75-85 parts of deionized water.

[0007] The concentrate additive comprises 25-40% by mass of organic alcohol amine, 20-35% by mass of fatty acid, 8-15% by mass of composite emulsifier, 12-18% by mass of lubricating anti-wear agent, 5-10% by mass of sodium ethylenediaminetetraacetate, and 1-2% by mass of defoaming agent.

[0008] The organic alcohol amine is triethanolamine or isopropanolamine; the fatty acid is tall oil acid or α-linolenic acid.

[0009] Furthermore, the composite emulsifier is prepared by compounding glycerol polyoxyethylene ether and sorbitan monostearate in a mass ratio of 1:1.

[0010] Furthermore, the defoaming agent is prepared by compounding castor oil polyoxyethylene ether and sorbitan fatty acid ester in a mass ratio of 1:1.

[0011] Furthermore, the lubricating and anti-wear agent is obtained by dissolving graphene oxide, triethanolamine and fatty alcohol polyoxyethylene ether in N,N-dimethylformamide in a mass ratio of 1:100:20 and reacting at 130° C. for 5 hours.

[0012] Furthermore, the preparation method of the vegetable oil-based hard water corrosion inhibitor is: Step (1), under nitrogen atmosphere, add hexadecanedioic acid and xylene to a reaction flask equipped with a condenser, a thermometer and a water separator, stir evenly, add N-(4-methoxyphenyl)ethylenediamine, react at 130-150° C. for 2-4 hours to carry out acylation reaction, then carry out cyclization reaction at 170-190° C. until no water flows out of the water separator, then heat to 220-240° C. and distill under reduced pressure, wash with tetrahydrofuran, and obtain a long-chain diacid imidazoline intermediate. The preparation reaction formula is as follows:

[0013] Step (2), under nitrogen atmosphere, add the long-chain diol imidazoline intermediate and N,N-dimethylformamide to the reaction flask, stir evenly, add sodium 2-bromoethane sulfonate, react at 90-110°C for 8-16h, add potassium hydroxide aqueous solution to adjust the pH to 7-9, concentrate under reduced pressure, wash with ethanol, then add boron tribromide and dichloromethane, react at 0-5°C for 12-24h, extract with ethyl acetate and deionized water, and concentrate to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate. The preparation reaction formula is as follows:

[0014] Step (3), adding epoxidized soybean oil and long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, adding 10-15 drops of fluoroboric acid dropwise under stirring, stirring for reaction, and after the reaction is completed, extracting with ethyl acetate and deionized water, and concentrating under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0015] Furthermore, in step (1), the molar ratio of hexadecanedioic acid to N-(4-methoxyphenyl)ethylenediamine is 1:2.1-2.3.

[0016] Furthermore, in step (2), the molar ratio of the long-chain diacid imidazoline intermediate, sodium 2-bromoethane sulfonate, and boron tribromide is 1:1.2-1.4:2.5-2.8.

[0017] Furthermore, in step (3), the mass ratio of the epoxidized soybean oil to the long-chain diol imidazoline quaternary ammonium salt intermediate is 100:10-30.

[0018] Furthermore, in step (3), the reaction temperature is 95-110° C. and the reaction time is 2-4 h.

[0019] Furthermore, the preparation method of the emulsified oil concentrate formula for the multifunctional hydraulic support is as follows: heat the deionized water to 35-45°C, mix evenly, add the organic alcohol amine, fatty acid, and composite emulsifier, stir evenly, add the lubricating anti-wear agent and sodium ethylenediaminetetraacetate, stir at 50-65°C for 40-60min, then add the vegetable oil-based anti-hard water corrosion inhibitor, stir at 500-800r / min for 1-2h, cool to below 30°C, add the defoaming agent, filter through a 10-20μm filter, and obtain the emulsified oil concentrate formula for the multifunctional hydraulic support.

[0020] Compared with the prior art, the present invention has the following beneficial effects: The invention uses hexadecanedioic acid and N-(4-methoxyphenyl)ethylenediamine as raw materials and sodium 2-bromoethanesulfonate as a quaternizing agent to synthesize a long-chain diol imidazoline quaternary ammonium salt intermediate, utilizes the hydroxyl group in the structure of the long-chain diol imidazoline quaternary ammonium salt intermediate to generate chemical bonding with the epoxy group of epoxidized soybean oil, and is compounded with organic alcohol amine, fatty acid, composite emulsifier and the like to obtain a multifunctional hydraulic support emulsified oil concentrate formula with good dispersibility, strong corrosion inhibition ability and strong extrusion wear resistance. The formula is green and environmentally friendly and can be industrially produced.

[0021] (1) The plant oil-based anti-hard water corrosion inhibitor contains bicyclic imidazoline and quaternary ammonium salt structure. The N atom of bicyclic imidazoline forms a coordination bond with the d orbital of iron to produce chemical adsorption. The hydrophobic long chain is oriented away from the metal surface, forming a dense hydrophobic film on the surface of cast iron, which can block the metal surface from corrosive media. + Ions can adsorb more additive molecules to the surface of cast iron through electrostatic interactions, thereby forming a dense physical and chemical adsorption film on the surface of cast iron, steel rods and copper rods, which effectively protects the surface of the metal matrix.

[0022] (2) Epoxidized soybean oil has a high viscosity index. During extrusion or friction, it is easy to form a lubricating film on the friction surface, which can effectively isolate the friction parts and significantly reduce the friction coefficient of the machine. At the same time, its viscosity-temperature performance is even better; the rigid benzene ring group structure gives the concentrate high thermal stability and chemical stability, making it difficult to decompose under high temperature and high pressure, and can maintain its lubricating properties for a long time. It is not easy to fail due to changes in temperature or pressure, which further extends the service life of the concentrate.

[0023] (3) The sodium sulfonate group in the plant oil-based hard water corrosion inhibitor can react with calcium, magnesium and other ions in hard water to form a water-soluble complex, effectively dispersing the metal ions in water, further enhancing its stability in hard water and improving its resistance to hard water.

[0024] (4) The concentrated liquid prepared by the present invention not only maintains the safety and freeze-thaw resistance of the existing emulsified oil, but also completely solves the problems of oil separation, soap separation, valve blockage, etc. of the emulsified oil. It can still maintain a fluid state at low temperatures and can recover quickly. At the same time, combined with the fact that epoxidized soybean oil is a renewable biological resource, non-toxic and environmentally friendly, it can meet the requirements of hydraulic supports for use under harsh working conditions. DETAILED DESCRIPTION

[0025] The compounds of the present invention and their preparation methods and applications are further described in detail below in conjunction with specific examples. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood. Unless otherwise indicated, the raw materials and reagents used in this application are all commercially available products, or can be prepared by known methods.

[0026] Hexadecanedioic acid, CAS number is 505-54-4.

[0027] N-(4-methoxyphenyl)ethylenediamine, CAS number is 24455-93-4.

[0028] Sodium 2-bromoethane sulfonate, CAS number is 4263-52-9.

[0029] Epoxidized soybean oil, CAS number is 8013-07-8.

[0030] Composite emulsifier: Glycerol polyoxyethylene ether and sorbitan monostearate are compounded in a mass ratio of 1:1.

[0031] Defoaming agent: castor oil polyoxyethylene ether and sorbitan fatty acid ester are compounded in a mass ratio of 1:1.

[0032] Lubricating anti-wear agent: Graphene oxide, triethanolamine and fatty alcohol polyoxyethylene ether are dissolved in N,N-dimethylformamide at a mass ratio of 1:100:20, and reacted at 130° C. for 5 hours to obtain the lubricating anti-wear agent.

[0033] Example 1

[0034] (1) Under nitrogen atmosphere, 85 mmol of hexadecanedioic acid and 340 mL of xylene were added to a reaction flask equipped with a condenser, a thermometer and a water separator. After stirring, 187 mmol of N-(4-methoxyphenyl)ethylenediamine was added and the mixture was reacted at 140°C for 3 h for acylation reaction. Then, a cyclization reaction was carried out at 180°C. When no water flowed out of the water separator, the mixture was heated to 230°C for vacuum distillation and washed with tetrahydrofuran to obtain a long-chain diacid imidazoline intermediate.

[0035] (2) Under nitrogen atmosphere, 82 mmol of the long-chain diacid imidazoline intermediate and 695 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 106.6 mmol of sodium 2-bromoethane sulfonate was added. The mixture was reacted at 100°C for 12 h. A potassium hydroxide aqueous solution was added to adjust the pH to 8. The mixture was concentrated under reduced pressure and washed with ethanol. Subsequently, 217.3 mol of boron tribromide and 1105 mL of dichloromethane were added. The mixture was reacted at 0°C for 16 h. The mixture was extracted with ethyl acetate and deionized water and concentrated to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate.

[0036] (3) Add 100 g of epoxidized soybean oil and 10 g of long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, add 12 drops of fluoroboric acid under stirring, react at 105 °C for 3 h, extract with ethyl acetate and deionized water, and concentrate under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0037] (4) Heat 85 g of deionized water to 40 °C, mix well, add 12 g of concentrated liquid additive, wherein the concentrated liquid additive includes 40% by weight of triethanolamine, 20% by weight of tall oil acid, 13% by weight of composite emulsifier, 15% by weight of lubricating anti-wear agent, 10% by weight of sodium ethylenediaminetetraacetate, and 2% by weight of defoaming agent, stir at 60 °C for 50 min, then add 3 g of vegetable oil-based anti-hard water corrosion inhibitor, stir at 600 r / min for 2 h, cool to below 30 °C, add defoaming agent, and filter through a 15 μm filter to obtain the emulsified oil concentrate formula for multifunctional hydraulic support.

[0038] Example 2

[0039] (1) Under nitrogen atmosphere, 120 mmol of hexadecanedioic acid and 360 mL of xylene were added to a reaction flask equipped with a condenser, a thermometer and a water separator. After stirring, 252 mmol of N-(4-methoxyphenyl)ethylenediamine was added and the mixture was reacted at 150°C for 2 h for acylation reaction. Then, a cyclization reaction was carried out at 190°C. When no water flowed out of the water separator, the mixture was heated to 240°C for vacuum distillation and washed with tetrahydrofuran to obtain a long-chain diacid imidazoline intermediate.

[0040] (2) Under nitrogen atmosphere, 105 mmol of the long-chain diacid imidazoline intermediate and 630 mL of N,N-dimethylformamide were added to the reaction flask. After stirring, 126 mmol of sodium 2-bromoethane sulfonate was added. The mixture was reacted at 110°C for 8 h. A potassium hydroxide aqueous solution was added to adjust the pH to 9. The mixture was concentrated under reduced pressure and washed with ethanol. Subsequently, 262.5 mol of boron tribromide and 1260 mL of dichloromethane were added. The mixture was reacted at 5°C for 12 h. The mixture was extracted with ethyl acetate and deionized water and concentrated to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate.

[0041] (3) Add 100 g of epoxidized soybean oil and 15 g of long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, add 10 drops of fluoroboric acid under stirring, react at 110 °C for 2 h, extract with ethyl acetate and deionized water, and concentrate under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0042] (4) Heat 82 g of deionized water to 45 °C, mix well, add 14 g of concentrated liquid additive, wherein the concentrated liquid additive includes 34% by weight of isopropanolamine, 22% by weight of α-linolenic acid, 15% by weight of a composite emulsifier, 18% by weight of a lubricating anti-wear agent, 10% by weight of sodium ethylenediaminetetraacetate, and 1% by weight of a defoaming agent, stir at 65 °C for 40 min, then add 4 g of a vegetable oil-based anti-hard water corrosion inhibitor, stir at 800 r / min for 1 h, cool to below 30 °C, add a defoaming agent, and filter through a 20 μm filter to obtain an emulsified oil concentrate formula for a multifunctional hydraulic support.

[0043] Example 3

[0044] (1) Under nitrogen atmosphere, 42 mmol of hexadecanedioic acid and 210 mL of xylene were added to a reaction flask equipped with a condenser, a thermometer and a water separator. After stirring, 96.6 mmol of N-(4-methoxyphenyl)ethylenediamine was added and the mixture was reacted at 130°C for 4 h for acylation reaction. Then, the mixture was reacted at 170°C for cyclization reaction. When no water flowed out of the water separator, the mixture was heated to 220°C for vacuum distillation and washed with tetrahydrofuran to obtain a long-chain diacid imidazoline intermediate.

[0045] (2) Under nitrogen atmosphere, 35 mmol of the long-chain diacid imidazoline intermediate and 350 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 49 mmol of sodium 2-bromoethane sulfonate was added. The mixture was reacted at 90°C for 16 h. A potassium hydroxide aqueous solution was added to adjust the pH to 7. The mixture was concentrated under reduced pressure and washed with ethanol. Then, 98 mol of boron tribromide and 525 mL of dichloromethane were added. The mixture was reacted at 0°C for 24 h. The mixture was extracted with ethyl acetate and deionized water and concentrated to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate.

[0046] (3) Add 100 g of epoxidized soybean oil and 20 g of long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, add 15 drops of fluoroboric acid under stirring, react at 95 °C for 4 h, extract with ethyl acetate and deionized water, and concentrate under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0047] (4) Heat 80 g of deionized water to 35 °C, mix well, add 15 g of concentrated liquid additive, wherein the concentrated liquid additive includes 25% by weight of triethanolamine, 35% by weight of tall oil acid, 15% by weight of composite emulsifier, 18% by weight of lubricating anti-wear agent, 6% by weight of sodium ethylenediaminetetraacetate, and 1% by weight of defoaming agent, stir at 50 °C for 60 min, then add 5 g of vegetable oil-based anti-hard water corrosion inhibitor, stir at 500 r / min for 2 h, cool to below 30 °C, add defoaming agent, and filter through a 20 μm filter to obtain the emulsified oil concentrate formula for multifunctional hydraulic support.

[0048] Example 4

[0049] (1) Under nitrogen atmosphere, 60 mmol of hexadecanedioic acid and 270 mL of xylene were added to a reaction flask equipped with a condenser, a thermometer and a water separator. After stirring, 135 mmol of N-(4-methoxyphenyl)ethylenediamine was added and the mixture was reacted at 145°C for 4 h for acylation reaction. Then, a cyclization reaction was carried out at 185°C. When no water flowed out of the water separator, the mixture was heated to 235°C for vacuum distillation and washed with tetrahydrofuran to obtain a long-chain diacid imidazoline intermediate.

[0050] (2) Under nitrogen atmosphere, 55 mmol of the long-chain diacid imidazoline intermediate and 420 mL of N,N-dimethylformamide were added to the reaction flask. After stirring, 74.8 mmol of sodium 2-bromoethane sulfonate was added. The mixture was reacted at 105°C for 12 h. A potassium hydroxide aqueous solution was added to adjust the pH to 8. The mixture was concentrated under reduced pressure and washed with ethanol. Subsequently, 146.3 mol of boron tribromide and 770 mL of dichloromethane were added. The mixture was reacted at 0°C for 15 h. The mixture was extracted with ethyl acetate and deionized water and concentrated to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate.

[0051] (3) Add 100 g of epoxidized soybean oil and 25 g of long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, add 14 drops of fluoroboric acid under stirring, react at 100 °C for 3 h, extract with ethyl acetate and deionized water, and concentrate under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0052] (4) Heat 78 g of deionized water to 40 °C, mix well, add 16 g of concentrated liquid additive, wherein the concentrated liquid additive includes 30% by weight of isopropanolamine, 32% by weight of α-linolenic acid, 8% by weight of a composite emulsifier, 18% by weight of a lubricating anti-wear agent, 10% by weight of sodium ethylenediaminetetraacetate, and 2% by weight of a defoaming agent, stir at 65 °C for 55 min, then add 6 g of a vegetable oil-based anti-hard water corrosion inhibitor, stir at 750 r / min for 2 h, cool to below 30 °C, add a defoaming agent, and filter through a 16 μm filter to obtain an emulsified oil concentrate formula for a multifunctional hydraulic support.

[0053] Example 5

[0054] (1) Under nitrogen atmosphere, 20 mmol of hexadecanedioic acid and 95 mL of xylene were added to a reaction flask equipped with a condenser, a thermometer and a water separator. After stirring, 44.8 mmol of N-(4-methoxyphenyl)ethylenediamine was added and the mixture was reacted at 145°C for 4 h for acylation reaction. Then, the mixture was reacted at 175°C for cyclization reaction. When no water flowed out of the water separator, the mixture was heated to 235°C for vacuum distillation and washed with tetrahydrofuran to obtain a long-chain diacid imidazoline intermediate.

[0055] (2) Under nitrogen atmosphere, 18 mmol of the long-chain diacid imidazoline intermediate and 155 mL of N,N-dimethylformamide were added to the reaction flask. After stirring evenly, 22.5 mmol of sodium 2-bromoethane sulfonate was added. The mixture was reacted at 95°C for 16 h. Aqueous potassium hydroxide solution was added to adjust the pH to 8. The mixture was concentrated under reduced pressure and washed with ethanol. Subsequently, 44.1 mol of boron tribromide and 260 mL of dichloromethane were added. The mixture was reacted at 5°C for 16 h. The mixture was extracted with ethyl acetate and deionized water and concentrated to obtain the long-chain diol imidazoline quaternary ammonium salt intermediate.

[0056] (3) Add 100 g of epoxidized soybean oil and 30 g of long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, add 15 drops of fluoroboric acid under stirring, react at 110 °C for 4 h, extract with ethyl acetate and deionized water, and concentrate under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

[0057] (4) Heat 75 g of deionized water to 45 °C, mix well, add 18 g of concentrated liquid additive, wherein the concentrated liquid additive includes 40% by weight of triethanolamine, 20% by weight of tall oil acid, 15% by weight of composite emulsifier, 15% by weight of lubricating anti-wear agent, 8% by weight of sodium ethylenediaminetetraacetate, and 2% by weight of defoaming agent, stir at 60 °C for 55 min, then add 7 g of vegetable oil-based anti-hard water corrosion inhibitor, stir at 650 r / min for 2 h, cool to below 30 °C, add defoaming agent, and filter through a 10 μm filter to obtain the emulsified oil concentrate formula for multifunctional hydraulic support.

[0058] Comparative Example 1 Heat 85g of deionized water to 40°C, mix evenly, add 15g of concentrated liquid additive, wherein the concentrated liquid additive includes 40% by weight of triethanolamine, 20% of tall oil acid, 13% of composite emulsifier, 15% of lubricating anti-wear agent, 10% of sodium ethylenediaminetetraacetate, and 2% of defoaming agent, stir at 60°C for 50min, cool to below 30°C, add defoaming agent, filter through a 15μm filter, and obtain the emulsified oil concentrate formula for hydraulic support.

[0059] Comparative Example 2 85g of OKS300 molybdenum disulfide mineral oil (purchased from Huangjiang Xinyuan Lubricant Business Department, Dongguan City), 8g of triethanolamine, 5g of sodium ethylenediaminetetraacetate and 2g of sodium nitrite were stirred at 60°C for 50min, cooled to below 30°C, added with a defoamer, and filtered through a 15μm filter to obtain emulsified oil for hydraulic support.

[0060] Anti-corrosion performance test: According to the technical requirements of coal industry standard MT76-2011 "Emulsified oil, concentrated liquid and high water content hydraulic fluid for hydraulic supports", the anti-corrosion performance of the emulsified oil concentrated liquid formula for hydraulic supports prepared in Examples 1-5 and Comparative Examples 1-2 was tested.

[0061] Table 1 Anti-corrosion performance test

[0062] From the test results in the above table, it can be seen that with the addition of the vegetable oil-based anti-hard water corrosion inhibitor, the concentrated solution has excellent anti-corrosion performance. This is because the vegetable oil-based anti-hard water corrosion inhibitor contains bicyclic imidazoline and quaternary ammonium salt structure, in which the N atom of bicyclic imidazoline and the d orbital of iron form a coordination bond to produce chemical adsorption, and the hydrophobic long chain is oriented away from the metal surface, forming a dense hydrophobic film on the cast iron surface, which can block the metal surface from corrosive media; the N in the quaternary ammonium salt structure + Ions can adsorb more additive molecules to the surface of cast iron through electrostatic interaction, thereby forming a dense physical and chemical adsorption film on the surface of cast iron, steel rods and copper rods, which effectively protects the surface of the metal substrate. Comparative Example 1 does not contain a vegetable oil-based anti-hard water corrosion inhibitor and has no anti-corrosion effect; Comparative Example 2 adds sodium nitrite as a corrosion inhibitor, and its anti-corrosion performance is average.

[0063] Extrusion anti-wear performance test: Referring to the technical requirements of the coal industry standard MT76-2011 "Emulsified oil, concentrated liquid and high water content hydraulic fluid for hydraulic supports", the test was carried out using a four-ball testing machine.

[0064] Table 2 Extrusion anti-wear performance test

[0065] From the test results in the above table, it can be seen that the extreme pressure and anti-wear performance of epoxy soybean oil is better than that of the mineral oil in Comparative Example 2. This is because the viscosity index of epoxy soybean oil is relatively large. During the extrusion or friction process, it is easy to form a lubricating film on the friction surface, which can effectively isolate the friction parts and significantly reduce the friction coefficient of the machine. At the same time, its viscosity-temperature performance is more excellent, because the rigid benzene ring group gives it high thermal stability and chemical stability, making it difficult to decompose under high temperature and high pressure, and can maintain its lubricating performance for a long time. It is not easy to fail due to changes in temperature or pressure, and further extends the service life of the concentrate.

[0066] Other performance tests: Tested according to the technical requirements of coal industry standard MT76-2011 "Emulsified oil, concentrated liquid and high water content hydraulic fluid for hydraulic supports".

[0067] Table 3 Other performance tests

[0068] The sodium sulfonate group in the vegetable oil-based anti-hard water corrosion inhibitor can react with calcium, magnesium and other ions in hard water to form a water-soluble complex, effectively dispersing metal ions in water, further enhancing its stability in hard water, and improving its hard water resistance. In addition to maintaining the safety and freeze-thaw resistance of existing emulsified oils, the concentrated solution prepared by the present invention also thoroughly solves the problems of oil separation, soap separation, valve blockage, etc. of emulsified oil, and remains in a flowing state at low temperatures, and can be quickly restored. Various surfactants are matched in different proportions, and functional corrosion-inhibiting monomers are added. Through directional adsorption and orderly association, the interface state is changed, so that the prepared concentrated solution has a wider range of applications and a longer service life.

[0069] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, but rather the present invention can be extended to all other methods and applications with the same functions.

Claims

1. The formula of emulsified oil concentrate for multifunctional hydraulic support is characterized by: The emulsified oil concentrate formula is composed of the following raw materials in parts by weight: 12-18 parts of concentrate additive, 3-7 parts of vegetable oil-based anti-hard water corrosion inhibitor and 75-85 parts of deionized water; The concentrate additive comprises 25-40% by mass of an organic alcohol amine, 20-35% by mass of a fatty acid, 8-15% by mass of a composite emulsifier, 12-18% by mass of a lubricating anti-wear agent, 5-10% by mass of sodium ethylenediaminetetraacetate, and 1-2% by mass of a defoaming agent; The organic alcohol amine is triethanolamine or isopropanolamine; the fatty acid is tall oil acid or α-linolenic acid.

2. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 1 is characterized in that: The composite emulsifier is prepared by compounding glycerol polyoxyethylene ether and sorbitan monostearate in a mass ratio of 1:

1.

3. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 1, characterized in that: The defoaming agent is prepared by compounding castor oil polyoxyethylene ether and sorbitan fatty acid ester in a mass ratio of 1:

1.

4. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 1, characterized in that: The lubricating and anti-wear agent is obtained by dissolving graphene oxide, triethanolamine and fatty alcohol polyoxyethylene ether in N,N-dimethylformamide at a mass ratio of 1:100:20 and reacting at 130° C. for 5 hours.

5. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 1, characterized in that: The preparation method of the vegetable oil-based hard water corrosion inhibitor is as follows: Step (1), under a nitrogen atmosphere, add hexadecanedioic acid and xylene to a reaction flask equipped with a condenser, a thermometer and a water separator, stir evenly, add N-(4-methoxyphenyl)ethylenediamine, react at 130-150° C. for 2-4 hours to carry out an acylation reaction, and then carry out a cyclization reaction at 170-190° C. until no water flows out of the water separator, then heat to 220-240° C. and distill under reduced pressure, wash with tetrahydrofuran, and obtain a long-chain diacid imidazoline intermediate; Step (2), under a nitrogen atmosphere, add a long-chain diol imidazoline intermediate and N,N-dimethylformamide to a reaction flask, stir evenly, add sodium 2-bromoethane sulfonate, react at 90-110° C. for 8-16 h, add potassium hydroxide aqueous solution to adjust the pH to 7-9, concentrate under reduced pressure, wash with ethanol, then add boron tribromide and dichloromethane, react at 0-5° C. for 12-24 h, extract with ethyl acetate and deionized water, and concentrate to obtain a long-chain diol imidazoline quaternary ammonium salt intermediate; Step (3), adding epoxidized soybean oil and long-chain diol imidazoline quaternary ammonium salt intermediate into a reaction flask, adding 10-15 drops of fluoroboric acid dropwise under stirring, stirring for reaction, and after the reaction is completed, extracting with ethyl acetate and deionized water, and concentrating under reduced pressure to obtain a vegetable oil-based anti-hard water corrosion inhibitor.

6. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 5, characterized in that: In the step (1), the molar ratio of hexadecanedioic acid to N-(4-methoxyphenyl)ethylenediamine is 1:2.1-2.

3.

7. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 5, characterized in that: In the step (2), the molar ratio of the long-chain diacid imidazoline intermediate, sodium 2-bromoethane sulfonate, and boron tribromide is 1:1.2-1.4:2.5-2.

8.

8. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 5, characterized in that: In the step (3), the mass ratio of the epoxidized soybean oil to the long-chain diol imidazoline quaternary ammonium salt intermediate is 100:10-30.

9. The formula of the emulsified oil concentrate for the multifunctional hydraulic support according to claim 5, characterized in that: In the step (3), the reaction temperature is 95-110° C. and the reaction time is 2-4 h.

10. A method for preparing a formula of an emulsified oil concentrate for a multifunctional hydraulic support, characterized in that: The preparation method comprises the following steps: heating deionized water to 35-45° C., mixing uniformly, adding organic alcohol amine, fatty acid and composite emulsifier, stirring uniformly, adding lubricating anti-wear agent and sodium ethylenediaminetetraacetate, stirring at 50-65° C. for 40-60 min, then adding vegetable oil-based anti-hard water corrosion inhibitor, stirring at 500-800 r / min for 1-2 h, cooling to below 30° C., adding defoaming agent, filtering through a 10-20 μm filter, and obtaining a formula of emulsified oil concentrate for a multifunctional hydraulic support.

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