Biodegradable emulsified oil for hydraulic support and preparation method thereof

Abstract

The invention belongs to the technical field of oil for hydraulic supports, and particularly relates to biodegradable emulsified oil for a hydraulic support and a preparation method of the biodegradable emulsified oil. The biodegradable emulsified oil for the hydraulic support is prepared from the following raw materials in parts by mass: 40 to 50 parts of modified castor oil, 2 to 6 parts of eutectic solvent, 2 to 5 parts of emulsifier, 3 to 8 parts of antirust agent, 0.5 to 1.5 parts of defoaming agent and 15 to 30 parts of water, the biodegradable emulsified oil for the hydraulic support, provided by the invention, has good compatibility with 40-grade artificial hard water, and also has excellent anti-rust property and corrosion resistance.

Description

Technical Field

[0001] This invention belongs to the field of hydraulic support oil technology, specifically relating to a biodegradable emulsified oil for hydraulic supports and its preparation method. Background Technology

[0002] Hydraulic supports are core equipment in coal mining, primarily functioning to support the roof, prevent collapses, and protect equipment and personnel. Hydraulic supports rely on a hydraulic system to transmit power and provide support for the hydraulic pillars. The hydraulic transmission medium is water-based hydraulic support concentrate or emulsified oil, which lubricates, prevents rust, and transmits power to the hydraulic system and support equipment.

[0003] Traditional emulsified oils for hydraulic supports are typically based on mineral oil, mixed with sodium petroleum sulfonate and ethylenediaminetetraacetate. After leakage, they are not easily decomposed in the environment and have a certain tendency to accumulate, polluting groundwater in the mine environment. With the increasing awareness of environmental protection in society, new biodegradable emulsified oils for hydraulic supports have become a research focus.

[0004] Currently, the base oils for biodegradable hydraulic support emulsions mainly include biodegradable synthetic esters and vegetable oils. For example, Chinese patent CN116590084B discloses a rapidly biodegradable hydraulic support emulsion. The raw materials, by weight, include: 2.0-12.0 parts synthetic ester, 3.0-15.0 parts surfactant, 4.0-15.0 parts corrosion and rust inhibitor, 2.0-8.0 parts complexing agent, 1.0-3.0 parts bactericide, 0.01-0.50 parts defoamer, 1.0-10.0 parts coupling agent, and 50.0-70.0 parts deionized water. This technical solution uses isooctyl oleate as a synthetic ester, which improves the biodegradability of the emulsion while also providing good lubricity and superior stability and hydrolytic stability compared to natural animal and vegetable oils. However, synthetic esters are relatively more expensive than vegetable oils.

[0005] Chinese Patent CN119979255B discloses a biodegradable emulsified oil for hydraulic supports made from natural plant extracts and its preparation method. First, through multi-step chemical modification of palm oil, including epoxidation, boronization, phosphating, and block polymerization, the epoxidation reaction introduces epoxy groups, improving the reactivity of the oil; boronization and phosphating reactions further enhance the polarity and lubricating film formation ability of the oil; and the block polymerization reaction with caprolactone enhances the stability and wear resistance of the lubricating film. Second, through carboxymethylation modification of chitosan, the carboxyl groups in carboxymethyl chitosan can react with oxides on the metal surface to form a chemical passivation protective film; the sulfonic acid groups in sodium lignosulfonate combine with the metal surface through electrostatic adsorption, further constructing a protective layer. The synergistic effect of both forms a multi-layered dense protective film on the metal surface, thereby significantly improving the anti-corrosion performance of the emulsified oil.

[0006] In practical applications, emulsified oil for hydraulic supports is generally diluted with local mine water at a rate of 3-5%. Although MT / T 76-2011 specifies that the sodium chloride content of hard water should be tested manually (330 mg / L), and that the water used for preparation should meet the requirements of being free of mechanical impurities and having a chloride ion content of no more than 200 mg / L, the actual mine water used in various coal mines is a complex system. In many parts of China, the mine water does not meet the preparation standards, and in some areas, the hardness of local groundwater can reach 2000 mg / L. Emulsified oil for hydraulic supports of general specifications cannot be fully adapted to this, and it is prone to instability during use, resulting in problems such as soap precipitation, flocculent matter, sediment, stratification, or water separation. The chloride ion content may even exceed 500 mg / L, resulting in poor rust and corrosion resistance.

[0007] However, the above-mentioned technical solutions and other existing technologies that use vegetable oil as the base oil for emulsified oil are only tested according to the corrosion resistance time of MT 76-2011 "Emulsified Oils, Concentrates and High Water Content Hydraulic Fluids for Hydraulic Supports". The test time is only 24 hours, which cannot simulate the actual long-term performance of emulsified oil. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a biodegradable emulsified oil for hydraulic supports and its preparation method. The biodegradable emulsified oil for hydraulic supports provided by the present invention has good compatibility with Grade 40 artificial hard water, and at the same time has excellent rust prevention and corrosion resistance.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a biodegradable emulsified oil for hydraulic supports, comprising the following raw materials in parts by weight: 40-50 parts modified castor oil, 2-6 parts eutectic solvent, 2-5 parts emulsifier, 3-8 parts rust inhibitor, 0.5-1.5 parts defoamer, and 15-30 parts water.

[0011] Furthermore, the method for preparing the modified castor oil includes the following steps: mixing castor oil, 6-amino-2-hydroxymethyl-n-hexane-1-ol and sodium hydroxide, and carrying out a first heating reaction to obtain pre-modified castor oil; mixing the pre-modified castor oil, toluene and p-toluenesulfonic acid, adding boric acid powder, and carrying out a second heating reaction under vacuum to obtain modified castor oil.

[0012] This invention first modifies castor oil with 6-amino-2-hydroxymethyl-n-hexane-1-ol, and then further modifies it with boric acid. By introducing amide bonds, long carbon chains, and boron atoms into the castor oil molecule, the thermal stability of castor oil can be effectively improved, allowing the modified castor oil to be firmly adsorbed onto the metal surface. This prevents the lubricating film of the emulsified oil from being damaged due to temperature rise during use, thereby improving the rust resistance and corrosion resistance of the emulsified oil.

[0013] Further, the mass ratio of 6-amino-2-hydroxymethyl-n-hexane-1-ol, castor oil, and sodium hydroxide is 0.1-0.2:1:0.01-0.02.

[0014] Furthermore, the mass ratio of the initially modified castor oil, toluene, p-toluenesulfonic acid, and boric acid is 15-20:2-5:0.1-0.3:10-15.

[0015] Furthermore, the temperature of the first heating reaction is 150-160℃, and the time is 6-7h.

[0016] In some alternative instances, the temperature of the first heating reaction may be 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, or 160°C, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0017] In some alternative instances, the duration of the first heating reaction may be 6 h, 6.1 h, 6.2 h, 6.3 h, 6.4 h, 6.5 h, 6.6 h, 6.7 h, 6.8 h, 6.9 h, or 7 h, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0018] Furthermore, the temperature of the second heating reaction is 140-150℃, and the time is 1-2 hours.

[0019] In some alternative instances, the temperature of the second heating reaction may be 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C, or 150°C, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0020] In some alternative instances, the duration of the second heating reaction may be 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 4.6 h, 2.7 h, 2.8 h, 2.9 h, or 3 h, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0021] Furthermore, the eutectic solvent is a mixture of ricinoleic acid and glycerol.

[0022] Furthermore, the molar ratio of ricinoleic acid to glycerol is 1-2:5-8.

[0023] This invention creatively prepares a eutectic solvent. The inventors discovered that the eutectic solvent prepared under the condition of a molar ratio of ricinoleic acid to glycerol of 1-2:5-8 can effectively improve the hard water resistance, rust prevention, and corrosion resistance of emulsified oil. This may be because the rich hydrogen bond network and polar effects of the eutectic solvent can effectively improve the solubility of modified castor oil while regulating the molecular arrangement of the emulsifier, so that the emulsifier molecules form a more ordered arrangement structure, improve the stability of the emulsifier, and thus improve the hard water resistance of the emulsified oil. In addition, it can be tightly adsorbed on the metal surface, thereby improving the lubricity and stability of the emulsified oil protective film.

[0024] In some alternative instances, the molar ratio of ricinoleic acid to glycerol may be 1:5, 1:6, 1:7, 1:8, 2:5, 2:6, 2:7, or 2:8, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0025] Furthermore, the method for preparing the eutectic solvent includes the following steps: mixing ricinoleic acid and glycerol, and heating and stirring at 60-80°C until the solution is completely clear and transparent.

[0026] Furthermore, the emulsifier is a mixture of isotridecyl alcohol polyoxyethylene polyoxypropylene ether and polyethylene glycol 400 phosphate monooleate.

[0027] Furthermore, the mass ratio of the isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether to the monooleate polyethylene glycol 400 phosphate is 0.8-1.2:0.3-0.7.

[0028] The emulsified oil provided by this invention has excellent compatibility with hard water of hardness grade 40. Another key technical solution to avoid problems such as soap precipitation, flocculent matter, sediment, stratification, or water separation lies in the selection of emulsifiers. The inventors found that the emulsified oil prepared by conventional nonionic emulsifiers such as nonylphenol polyoxyethylene ether and sorbitan monostearate does not have the compatibility with hard water of hardness grade 40 as expected. Instead, it becomes unstable after being placed at 70±2℃ for 168 hours.

[0029] In some alternative instances, the mass ratio of the isotridecyl alcohol polyoxyethylene polyoxypropylene ether to polyethylene glycol 400 phosphate monooleate may be 0.8:0.7, 0.9:0.6, 1:0.5, 1.1:0.4 or 1.2:0.3, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0030] Furthermore, the rust inhibitor is selected from at least one of polycarboxylic acid amine salts, benzotriazole, and triethanolamine borate.

[0031] Furthermore, the defoamer is selected from at least one of silicone defoamers, polyether defoamers, and mineral oil defoamers.

[0032] Secondly, the present invention provides a method for preparing the above-mentioned biodegradable hydraulic support emulsified oil, comprising the following steps: mixing emulsifier and water, adding eutectic solvent and modified castor oil, mixing, and then adding defoamer and rust inhibitor and stirring evenly to obtain the final product.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The emulsified oil provided by this invention has good compatibility with Grade 40 artificial hard water. After being placed at 70±2℃ for 168 hours, there is no soap separation, flocculent matter, sediment, stratification, or water separation.

[0035] 2. The emulsified oil provided by this invention has excellent rust prevention and corrosion resistance. Cast iron did not show rust or discoloration after a temperature of 35±2℃ for 168 hours, and steel bars and brass bars did not show rust or discoloration after a temperature of 70±2℃ for 720 hours.

[0036] 3. The emulsified oil provided by the present invention also has the advantages of being biodegradable, having good lubricity, freeze-thaw resistance, and defoaming properties. Attached Figure Description

[0037] Figure 1 This is a physical image of the biodegradable hydraulic support emulsion oil from Example 1. Detailed Implementation

[0038] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0039] Unless otherwise specified, the raw materials, reagents or apparatus used in the following examples and comparative examples are available from conventional commercial sources or can be obtained by existing known methods.

[0040] Preparation Example 1

[0041] This preparation example provides modified castor oil:

[0042] 1 kg of castor oil, 0.15 kg of 6-amino-2-hydroxymethyl-n-hexane-1-ol, and 15 g of sodium hydroxide were mixed and stirred evenly at 150 °C. The mixture was then subjected to a first heating reaction for 7 h to obtain pre-modified castor oil. 0.8 kg of pre-modified castor oil, 0.2 kg of toluene, and 5 g of p-toluenesulfonic acid were mixed and stirred evenly at 140 °C. 0.6 kg of boric acid powder was then added, and the mixture was subjected to a second heating reaction under vacuum for 2 h to obtain modified castor oil.

[0043] Castor oil is sourced from Shanghai Mengtong Chemical Co., Ltd., and is of superior grade.

[0044] Preparation Example 2

[0045] This preparation example provides modified castor oil:

[0046] 1 kg of castor oil, 0.15 kg of diethanolamine, and 15 g of sodium hydroxide were mixed and stirred evenly at 150 °C. The mixture was then subjected to a first heating reaction for 7 h to obtain pre-modified castor oil. 0.8 kg of pre-modified castor oil, 0.2 kg of toluene, and 5 g of p-toluenesulfonic acid were mixed and stirred evenly at 140 °C. 0.6 kg of boric acid powder was then added, and the mixture was subjected to a second heating reaction under vacuum for 2 h to obtain modified castor oil.

[0047] Castor oil is sourced from Shanghai Mengtong Chemical Co., Ltd., and is of superior grade.

[0048] Preparation Example 3

[0049] This preparation example provides a eutectic solvent:

[0050] The solution is prepared by mixing ricinoleic acid and glycerol in a molar ratio of 1:6 and heating and stirring at 70°C until the solution is completely clear and transparent.

[0051] Preparation Example 4

[0052] This preparation example provides a eutectic solvent:

[0053] The solution is prepared by mixing ricinoleic acid and glycerol in a molar ratio of 1:9 and heating and stirring at 70°C until the solution is completely clear and transparent.

[0054] Preparation Example 5

[0055] This preparation example provides a eutectic solvent:

[0056] The solution is prepared by mixing ricinoleic acid and glycerol in a molar ratio of 3:4 and heating and stirring at 70°C until the solution is completely clear and transparent.

[0057] Example 1

[0058] This embodiment provides a biodegradable emulsified oil for hydraulic supports, comprising the following raw materials in parts by weight: 42 parts of modified castor oil from Preparation Example 1, 3 parts of eutectic solvent from Preparation Example 3, 3 parts of emulsifier, 4 parts of rust inhibitor, 0.8 parts of defoamer, and 20 parts of water.

[0059] The emulsifier is a mixture of isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether and polyethylene glycol 400 phosphate monooleate in a mass ratio of 1:0.5.

[0060] The isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether is sourced from Hangzhou Kecheng Chemical Co., Ltd., model number: TF-70.

[0061] The monooleate polyethylene glycol 400 phosphate was sourced from Nantong Hansheng Chemical Co., Ltd., and its model number is PEG400MO phosphate.

[0062] The rust inhibitor is a polycarboxylic acid amine salt, sourced from Dexu New Materials (Guangzhou) Co., Ltd., model: DX307.

[0063] The defoamer is a polyether defoamer, sourced from Guangdong Tianfeng Defoamer Co., Ltd., model: DP-69.

[0064] The preparation method of the above-mentioned biodegradable hydraulic support emulsified oil includes the following steps: mixing emulsifier and water, adding eutectic solvent and modified castor oil, mixing, and then adding defoamer and rust inhibitor and stirring evenly to obtain the final product.

[0065] Example 2

[0066] This embodiment provides a biodegradable emulsified oil for hydraulic supports, comprising the following raw materials in parts by weight: 45 parts of modified castor oil from Preparation Example 1, 4 parts of eutectic solvent from Preparation Example 3, 4 parts of emulsifier, 6 parts of rust inhibitor, 1.2 parts of defoamer, and 25 parts of water.

[0067] The emulsifier is a mixture of isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether and polyethylene glycol 400 phosphate monooleate in a mass ratio of 1:0.5.

[0068] The isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether is sourced from Hangzhou Kecheng Chemical Co., Ltd., model number: TF-70.

[0069] The monooleate polyethylene glycol 400 phosphate was sourced from Nantong Hansheng Chemical Co., Ltd., and its model number is PEG400MO phosphate.

[0070] The rust inhibitor is a polycarboxylic acid amine salt, sourced from Dexu New Materials (Guangzhou) Co., Ltd., model: DX307.

[0071] The defoamer is a polyether defoamer, sourced from Guangdong Tianfeng Defoamer Co., Ltd., model: DP-69.

[0072] The preparation method of the above-mentioned biodegradable hydraulic support emulsified oil includes the following steps: mixing emulsifier and water, adding eutectic solvent and modified castor oil, mixing, and then adding defoamer and rust inhibitor and stirring evenly to obtain the final product.

[0073] Example 3

[0074] This embodiment provides a biodegradable emulsified oil for hydraulic supports, comprising the following raw materials in parts by weight: 50 parts of modified castor oil from Preparation Example 1, 6 parts of eutectic solvent from Preparation Example 3, 5 parts of emulsifier, 8 parts of rust inhibitor, 1.5 parts of defoamer, and 30 parts of water.

[0075] The emulsifier is a mixture of isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether and polyethylene glycol 400 phosphate monooleate in a mass ratio of 1:0.5.

[0076] The isomeric tridecyl alcohol polyoxyethylene polyoxypropylene ether is sourced from Hangzhou Kecheng Chemical Co., Ltd., model number: TF-70.

[0077] The monooleate polyethylene glycol 400 phosphate was sourced from Nantong Hansheng Chemical Co., Ltd., and its model number is PEG400MO phosphate.

[0078] The rust inhibitor is a polycarboxylic acid amine salt, sourced from Dexu New Materials (Guangzhou) Co., Ltd., model: DX307.

[0079] The defoamer is a polyether defoamer, sourced from Guangdong Tianfeng Defoamer Co., Ltd., model: DP-69.

[0080] The preparation method of the above-mentioned biodegradable hydraulic support emulsified oil includes the following steps: mixing emulsifier and water, adding eutectic solvent and modified castor oil, mixing, and then adding defoamer and rust inhibitor and stirring evenly to obtain the final product.

[0081] Comparative Example 1

[0082] This comparative example provides a biodegradable emulsified oil for hydraulic supports, which differs from Example 2 only in that the modified castor oil of Preparation Example 1 is replaced with an equal mass fraction of the modified castor oil of Preparation Example 2; all other aspects are the same.

[0083] Comparative Example 2

[0084] This comparative example provides a biodegradable emulsified oil for hydraulic supports, which differs from Example 2 only in that the modified castor oil in Preparation Example 1 is replaced with an equal mass of castor oil; all other aspects are the same.

[0085] Comparative Example 3

[0086] This comparative example provides a biodegradable emulsified oil for hydraulic supports, which differs from Example 2 only in that the eutectic solvent of Preparation Example 3 is replaced with an equal mass fraction of the eutectic solvent of Preparation Example 4; all other aspects are the same.

[0087] Comparative Example 4

[0088] This comparative example provides a biodegradable emulsified oil for hydraulic supports, which differs from Example 2 only in that the eutectic solvent of Preparation Example 3 is replaced with an equal mass fraction of the eutectic solvent of Preparation Example 5; all other aspects are the same.

[0089] Comparative Example 5

[0090] This comparative example provides a biodegradable emulsified oil for hydraulic supports, which differs from Example 2 only in that the eutectic solvent in Preparation Example 3 is replaced with an equal mass fraction of water; all other aspects are the same.

[0091] Comparative Example 6

[0092] This comparative example provides a biodegradable emulsified oil for hydraulic supports. The only difference from Example 2 is that isotridecyl alcohol polyoxyethylene polyoxypropylene ether is replaced with an equal mass fraction of nonylphenol polyoxyethylene ether, sourced from Taixing Lingfei Chemical Technology Co., Ltd., model: TX-7; all other aspects are the same.

[0093] Comparative Example 7

[0094] This comparative example provides a biodegradable emulsified oil for hydraulic supports. The only difference from Example 2 is that the polyethylene glycol monooleate 400 phosphate is replaced with an equal mass fraction of sorbitan monostearate, sourced from Hangzhou Kecheng Chemical Co., Ltd., model: S-20; all other aspects are the same.

[0095] Comparative Example 8

[0096] This comparative example provides a biodegradable emulsified oil for hydraulic supports. The only difference from Example 2 is that the emulsifier is glycerol polyoxyethylene ether (Tongxiang Henglong Chemical Co., Ltd., model: glycerol (18.5) ether) and sorbitan monostearate in a mass ratio of 1:1; all other aspects are the same.

[0097] Performance testing:

[0098] 1. Mix the above emulsified oil and Grade 40 artificial hard water at a volume ratio of 95:5. After mixing, place the mixture at 70±2℃ for 168 hours and observe whether soap separation, flocculent matter, sediment, stratification, or water separation occurs.

[0099] 2. Mix the above-mentioned emulsified oil and Grade 40 artificial hard water at a volume ratio of 95:5. After mixing, conduct rust prevention tests on cast iron according to standard MT76-2011 "Emulsified Oil, Concentrated Oil and High Water Content Hydraulic Fluid for Hydraulic Supports". The rust prevention test temperature is 35±2℃ and the time is 168h. Conduct corrosion prevention tests on steel bars, brass bars and zinc bars. The corrosion prevention test temperature is 70±2℃ and the time is 720h.

[0100] The results are shown in Table 1.

[0101] Table 1

[0102]

[0103] Table 1 shows that the diluted solution after diluting the emulsified oil with Grade 40 artificial hard water is as follows:

[0104] The emulsified oils in Examples 1-3 exhibit good compatibility with Grade 40 artificial hard water. After being placed at 70±2℃ for 168 hours, no soap precipitation, flocculent matter, sediment, stratification, or water separation occurs. They also demonstrate excellent rust and corrosion resistance. Cast iron showed no rust or discoloration after being placed at 35±2℃ for 168 hours, while steel and brass rods showed no rust or discoloration after being placed at 70±2℃ for 720 hours.

[0105] Comparative Example 1 used castor oil modified with diethanolamine and boric acid. The resulting emulsion oil showed a decrease in rust and corrosion resistance. This may be because diethanolamine lacks a long carbon chain compared to 6-amino-2-hydroxymethyl-n-hexane-1-ol, resulting in a decrease in adsorption effect.

[0106] Comparative Example 2 used epoxy-modified castor oil, which resulted in a decrease in the compatibility of the emulsified oil with Grade 40 artificial hard water, the appearance of soap precipitation and flocculent matter, and a significant decrease in rust prevention and corrosion resistance.

[0107] The proportions of eutectic flux in Comparative Examples 3 and 4 are outside the scope of protection of this invention, resulting in decreased compatibility of the emulsified oil with Grade 40 artificial hard water, soap precipitation, and a significant decrease in rust and corrosion resistance.

[0108] In Comparative Example 5, the absence of a low eutectic flux resulted in decreased compatibility of the emulsified oil with Grade 40 artificial hard water, leading to soap precipitation, flocculent matter, and a significant reduction in rust and corrosion resistance.

[0109] The composition of the emulsifier in Comparative Examples 6-8 was changed, resulting in decreased compatibility of the emulsified oil with Grade 40 artificial hard water, the appearance of soap precipitation and flocculent matter, and a significant decrease in rust prevention and corrosion resistance.

[0110] 3. The lubricity, freeze-thaw resistance and defoaming properties of the emulsified oils in Examples 1-3 were tested according to the standard MT 76-2011 "Emulsified Oils, Concentrated Oils and High Water Content Hydraulic Fluids for Hydraulic Supports". The results are shown in Table 2.

[0111] Table 2

[0112]

[0113] As can be seen from Table 2, the emulsified oils provided in Examples 1-3 of the present invention have good lubricity, freeze-thaw resistance and defoaming properties, which all meet the requirements of standard MT 76-2011 "Emulsified oils, concentrated oils and their high water content hydraulic fluids for hydraulic supports".

[0114] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A biodegradable emulsified oil for hydraulic support characterized by comprising: a base oil; a surfactant; and a biodegradable additive. The raw materials include the following quality parts: modified castor oil 40-50 parts, eutectic solvent 2-6 parts, emulsifier 2-5 parts, anti-rust agent 3-8 parts, defoaming agent 0.5-1.5 parts, and water 15-30 parts; The preparation method of the modified castor oil comprises the following steps: mixing castor oil, 6-amino-2-hydroxymethyl n-hexane-1-alcohol and sodium hydroxide, performing a first heating reaction to obtain initial modified castor oil; mixing the initial modified castor oil, toluene and p-toluenesulfonic acid, adding boric acid powder, performing a second heating reaction under vacuum to obtain the modified castor oil.

2. The biodegradable emulsified oil for hydraulic support according to claim 1, characterized by, The mass ratio of the 6-amino-2-hydroxymethyl n-hexane-1-alcohol, castor oil and sodium hydroxide is 0.1-0.2:1:0.01-0.02; the mass ratio of the initial modified castor oil, toluene, p-toluenesulfonic acid and boric acid powder is 15-20:2-5:0.1-0.3:10-15.

3. The biodegradable emulsified oil for hydraulic support according to claim 2, characterized by, The temperature of the first heating reaction is 150-160 DEG C, and the time is 6-7 h; the temperature of the second heating reaction is 140-150 DEG C, and the time is 1-2 h.

4. The biodegradable emulsified oil for hydraulic support according to claim 1, characterized by, The eutectic solvent is a mixture of ricinoleic acid and glycerol.

5. The biodegradable emulsified oil for hydraulic support according to claim 4, characterized by, The molar ratio of the ricinoleic acid and glycerol is 1-2:5-8.

6. The biodegradable emulsified oil for hydraulic support according to claim 1, characterized by, The emulsifier is a mixture of isomeric tridecanol polyoxyethylene polyoxypropylene ether and monooleate polyethylene glycol 400 phosphate ester.

7. The biodegradable emulsified oil for hydraulic support according to claim 6, characterized by, The mass ratio of the isomeric tridecanol polyoxyethylene polyoxypropylene ether and monooleate polyethylene glycol 400 phosphate ester is 0.8-1.2:0.3-0.

7.

8. The biodegradable emulsified oil for hydraulic support according to any one of claims 1 to 7, characterized by, The anti-rust agent is selected from at least one of polycarboxylic acid amine salt, benzotriazole and triethanolamine borate.

9. The biodegradable emulsified oil for hydraulic support according to any one of claims 1 to 7, characterized by, The defoaming agent is selected from at least one of organic silicon defoaming agent, polyether defoaming agent and mineral oil defoaming agent.

10. The method of producing the biodegradable emulsified oil for hydraulic support according to any one of claims 1 to 9, characterized by, The method comprises the following steps: mixing the emulsifier and water, adding the eutectic solvent and modified castor oil, and then adding the defoaming agent and anti-rust agent and stirring uniformly.

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