Concentrated solution for high-hard-water-resistant hydraulic support

Abstract

The invention relates to a high-hardness-water-resistant hydraulic support concentrated solution which is prepared from the following components in percentage by mass: 4%-10% of boric acid ester, 1%-3% of tall oil imidazoline sulfonate, 0.5%-1.5% of benzimidazole, 1%-5% of triethanolamine, 1%-4% of fatty alcohol-polyoxyethylene ether carboxylic acid, 1%-3% of alkyl carboxylic acid isomeric polyol amine soap and the balance of water. 1%-3% of an anti-hard water agent and the balance of water. The concentrated solution for the hydraulic support can tolerate 2,000 ppm of hard water, all the raw materials can be biodegraded, and the anti-rust and anti-corrosion performance is excellent. The concentrated solution for the hydraulic support is simple in preparation process, low in raw material cost and suitable for industrial large-scale production.

Description

Technical Field

[0001] The invention belongs to the field of transmission medium for coal mine hydraulic supports, and in particular relates to a concentrated liquid for hydraulic supports and a preparation method thereof. Background Art

[0002] Concentrated liquid for hydraulic supports is a kind of substance that uses water as the base liquid to form a solution-type diluent. It is generally composed of water, water-soluble rust inhibitors, corrosion inhibitors, lubricants and other additives, and is a thermodynamically stable system with solubilization. With the implementation of the new industry standard MT76-2011 "Emulsified oil, concentrated liquid and high-water content hydraulic fluid for hydraulic supports", manufacturers of emulsified oil or concentrated liquid for hydraulic supports need to continuously improve production processes and perfect their performance indicators to meet the needs of comprehensive mechanized mining in actual mines.

[0003] The amount of water used for preparing the transmission medium of hydraulic supports is huge, especially in the mining areas in the northern region where there is a serious water shortage, and the water quality is complex and changeable, with high hardness, resulting in a mismatch between the concentrate model and the water quality of the water used for preparing the liquid, which seriously affects the use effect of the product and the safe and stable operation of the hydraulic supports. In order to ensure the performance of the concentrated liquid for hydraulic supports, the common practice is to add the anti-hard water agent EDTA. For example, Chinese patent CN 105838494 B discloses a concentrated liquid for hydraulic supports, and the components and mass percentages are: 25-40% glycerol, 2-5% rust inhibitor, 5-20% lubricating compound, 5-10% emulsifying compound, 10-20% rust and corrosion resistant water, 0.5-5% EDTA-2Na water softener, and 15-30% water. However, EDTA is an organic complexing agent, and the hardness of mine water often fluctuates greatly. When the hardness of mine water increases and exceeds the complexing capacity of the high-water hydraulic fluid of the hydraulic support, it will cause the high-water hydraulic fluid to precipitate soap, produce floccules and sediments, and then block the hydraulic system, causing the hydraulic support to fail to operate normally. To this end, Chinese patent CN 107057821 A proposes an improved environmentally friendly emulsified oil for hydraulic supports by changing the formula ratio and some components. The main components and mass percentages of the emulsified oil are 5-10% glycerol, 4-6% rust inhibitor, 10-20% lubricating compound, 5-10% emulsifying compound, 15-25% rust-proof and anti-corrosion water, and sodium hydroxide, EDTA-2Na, sodium citrate, antioxidant, bactericide, defoamer, pigment and water. The patented technology claims that no oil or soap precipitation occurs during use. However, since the organic complexing agent EDTA is used in its formula, the technical problems existing in the use of EDTA are not fundamentally changed. According to actual production experience, its use is only suitable for situations where the mine water hardness is low and the water quality is stable.

[0004] In addition, sodium nitrite is commonly used as an anti-rust and anti-corrosion agent in the hydraulic support fluid of the prior art, such as the Chinese patent CN

[0005] 101029273B provides a liquid concentrate for hydraulic support, which is composed of: water, sodium sulfonate, triethanolamine, Tween-80, benzotriazole, disodium ethylenediaminetetraacetic acid, OS-15, NaNO2, sodium benzoate, and antifoaming agent. In the product formula of the hydraulic support liquid disclosed in Chinese patent CN117186978A, sodium nitrite (NaNO2) is also added as an anti-rust and anti-corrosion agent. However, NaNO2 is a strong carcinogen recognized by countries around the world. Long-term use not only seriously affects the health of underground workers, but also has a long-term potential impact on groundwater in mining areas. Although EDTA or NaNO2 is not used in the patented technology of a hard water-resistant lubricant, a concentrated liquid for hydraulic support and a preparation method thereof disclosed in Chinese patent CN 114214103 B, the patented technology uses graphene oxide to modify a polyether lubricant to prepare a hard water-resistant lubricant, and then uses the hard water-resistant lubricant to prepare a hydraulic support concentrated liquid. However, the preparation process of graphene oxide is complicated, costly and highly toxic. Studies have shown that graphene oxide has varying degrees of harm to the human respiratory system, cardiovascular system, nervous system, reproductive system, skin, eyes, etc. In addition, in groundwater with low concentrations of organic matter, graphene oxide nanoparticles will also increase the hardness of the water body, which has potential adverse effects on the groundwater environment and bacteria. Therefore, its practical application is greatly limited.

[0006] The aforementioned hydraulic support hydraulic fluid (or concentrate) is difficult to promote and apply. Therefore, it is urgent to develop environmentally friendly and safe hydraulic fluid for hydraulic supports. Chinese patent CN 114989879 A discloses an environmentally friendly synthetic hydraulic support concentrate, which is composed of: 90-110 parts of base oil; 1.1-11 parts of reaction preparation; 0.5-2.5 parts of anti-wear agent; 0.5-2.5 parts of antioxidant; 0.5-5 parts of viscosity regulator; 3.5-10 parts of metal chelating agent; it uses Class IV and Class V base oils as base oils, and uses esterification reaction to remove free fatty acids in ester oils to extend the service life of the product. Chinese patent CN 114686293B provides a high hardness water resistant hydraulic support concentrate and its preparation method, wherein the hydraulic support concentrate is composed of: hydroxy cellulose: 2-10%; long chain dibasic acid polyethylene glycol ester: 2-10%; water-soluble polyvinyl alcohol: 2-5%; monoethanolamine: 2-5%; water-based polyurethane: 2-5%; boric acid: 2-5%; octanoic acid: 1-5%; ethylene glycol: 1-5%; benzotriazole: 0.05%-0.1%; hydrophilic modified nano carbon microspheres: 0.01-0.03%; the balance is tap water. The above patent technology has the disadvantages of complex formula ingredients, some raw material ingredients are expensive and difficult to obtain, and difficult to recycle, so it is difficult to promote. Summary of the invention

[0007] In order to solve the problems in the prior art that the concentrated liquid for hydraulic supports is not suitable for its formulation, has serious environmental problems or has poor use effect, and the problems of complicated preparation process, high cost and being unfavorable for popularization and application caused by inappropriate formulation selection, the purpose of the present invention is to provide an environmentally friendly concentrated liquid for hydraulic supports with high resistance to hard water.

[0008] The concentrated liquid for hydraulic supports of the present invention not only meets the technical requirements of the coal industry standard MT76-2011 "Emulsified oil, concentrated liquid and high-water content hydraulic fluid for hydraulic supports", but also has safe and non-toxic formula components, good biodegradability and excellent hard water resistance. At the same time, according to the formula scheme of the present invention, the preparation process of the concentrated liquid for hydraulic supports provided by the present invention is simple and low in cost, which meets the requirements of industrial large-scale production.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions.

[0010] A concentrated liquid for a hydraulic support resistant to high hardness water, comprising the following components in percentage by mass:

[0011]

[0012]

[0013] In the formula of the concentrated solution for the anti-high-hardness water hydraulic support of the present invention, boric acid ester has good water solubility, rust and corrosion resistance and lubricity, but when used alone, to ensure its rust and corrosion resistance, the addition amount must be at least 20%. The inventors have found that if boric acid ester is compounded with tall oil imidazoline sulfonate, benzimidazole and triethanolamine, the addition amount of boric acid ester can be greatly reduced while ensuring that the product has good rust and corrosion resistance, indicating that there is an obvious synergistic effect between boric acid ester and tall oil imidazoline sulfonate, benzimidazole and triethanolamine, and as a result, the rust and corrosion resistance of the concentrated solution for the anti-high-hardness water hydraulic support of the present invention is improved.

[0014] In the formula of the concentrated liquid for high-hardness water resistant hydraulic support of the present invention, tall oil imidazoline sulfonate has the function of an amphoteric surfactant, which is green, environmentally friendly and easily biodegradable; fatty alcohol polyoxyethylene ether carboxylic acid has the function of a multifunctional anionic surfactant, which has excellent hard water resistance and is non-toxic and easily biodegradable; alkyl carboxylic acid isomeric polyol amine soap has the function of a non-ionic surfactant, which is non-toxic and completely biodegradable, and the addition of this component in the formula can play a good defoaming role. The combination of the composite system of multiple surfactants and the hard water resistance of sodium gluconate, tetrasodium glutamate diacetate or trisodium methylglycine diacetate with biodegradable properties further improves the hard water resistance of the product.

[0015] In some embodiments of the present invention, the borate is preferably a combination of two or more of tall oil diethanolamide borate, oleic acid diethanolamide borate, triethanolamide borate, and stearic acid diethanolamide borate. A preferred embodiment is that the mass ratio of borate to tall oil imidazoline sulfonate, benzimidazole, and triethanolamine is 2-4:1-3:0.5-1:1-3.

[0016] In some embodiments of the present invention, the anti-hard water agent is a combination of two or more of sodium gluconate, tetrasodium glutamate diacetate and trisodium methylglycine diacetate.

[0017] The method for preparing the concentrated liquid for the high hardness water resistant hydraulic support of the present invention comprises the following steps:

[0018] Step 1, first add borate, tall oil imidazoline sulfonate, benzimidazole and triethanolamine into water according to proportion, and heat and stir to obtain a clear mixed solution;

[0019] Step 2: Add fatty alcohol polyoxyethylene ether sulfonate, alkyl carboxylic acid isomeric polyol amine soap and anti-hard water agent to the mixed solution obtained in step 1, heat and stir to obtain a fully biodegradable concentrated solution for hydraulic support.

[0020] Preferably, in step 1, the heating and stirring temperature is 30 to 50° C., and the stirring time is 10 to 15 min.

[0021] Preferably, in step 2, the heating and stirring temperature is 20 to 40° C., and the stirring time is 20 to 40 min.

[0022] The preparation method of the concentrated liquid for hydraulic supports in the embodiment of the present invention is simple, the production equipment is simple, the raw material cost is low, the reaction conditions are mild, the energy consumption is low, and it is suitable for industrial large-scale production. The prepared concentrated liquid for hydraulic supports has excellent biodegradability, hard water resistance, rust and corrosion resistance, and outstanding lubrication performance.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0024] (1) The concentrated liquid formula for the hydraulic support of the present invention does not contain EDTA, an anti-hard water agent that is difficult to biodegrade, and adopts a compound of multiple surfactants, which is combined with anti-hard water agents such as sodium gluconate, tetrasodium glutamate diacetate, and trisodium methylglycine diacetate that have biodegradable properties. This not only improves the anti-hard water performance of the product, but also makes the product of the present invention more environmentally friendly.

[0025] (2) The formula composition of the concentrated liquid for hydraulic supports of the present invention does not contain additives such as nitrite and graphene oxide, thereby overcoming the problems that the existing concentrated liquid products for hydraulic supports may cause the occurrence of hydraulic liquid soap, the generation of floccules and sediments, and the blockage of the hydraulic system, causing the hydraulic supports to fail to operate normally, or the effects of toxic and harmful non-biodegradable components on human health and potential harm to the environment. In the formula of the concentrated liquid for hydraulic supports of the present invention, each component has good biodegradability and is non-toxic, so that the concentrated liquid for hydraulic supports of the present invention also has obvious green environmental protection performance.

[0026] (3) In the formula of the concentrated liquid for hydraulic support of the present invention, by optimizing the composition and the proportion of each component, when the mass ratio of boric acid ester to tall oil imidazoline sulfonate, benzotriazole, and triethanolamine is 2-4:1-3:0.5-1:1-3, it not only has good anti-rust and anti-corrosion functions, but also has certain lubricating properties; 1%-4% (wt.%) fatty alcohol polyoxyethylene ether carboxylic acid and 1%-3% (wt.%) alkyl carboxylic acid isomeric polyol amine soap components are added. Among them, fatty alcohol polyoxyethylene ether carboxylic acid has a multifunctional anionic surfactant function and exhibits a strong resistance to hard water; alkyl carboxylic acid isomeric polyol amine soap has a non-ionic surfactant function and has good solubility in hard water systems. It not only has a defoaming effect, but also can effectively reduce the friction coefficient of the system and reduce equipment loss. When 1% to 4% (wt.%) of fatty alcohol polyoxyethylene ether carboxylic acid, 1% to 3% (wt.%) of alkyl carboxylic acid isomeric polyol amine soap, 4% to 10% (wt.%) of boric acid ester, 1% to 3% (wt.%) of tall oil imidazoline sulfonate, 0.5% to 1.5% (wt.%) of benzimidazole and 1% to 5% (wt.%) of triethanolamine are used in combination, the hard water resistance of the concentrated liquid product for hydraulic support can be enhanced, and the lubrication performance and anti-rust function of the concentrated liquid can be enhanced. At the same time, the production equipment of the concentrated liquid for hydraulic support of the present invention is simple, the reaction conditions are mild, the energy consumption is low, and it is suitable for large-scale industrial production. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention is clearly and completely described below. Obviously, the described embodiment is a part of the embodiment of the present invention, not all. Based on the described embodiment, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the present invention.

[0028] The technical or scientific terms used in the present invention should have the common meanings that can be understood by those having ordinary skills in the field to which the present invention belongs.

[0029] In one aspect, an embodiment of the present invention provides a concentrated liquid for a hydraulic support, wherein the concentrated liquid for a hydraulic support comprises the following components in percentage by mass:

[0030]

[0031] The boric acid ester is a kind of ester with good water solubility, rust and corrosion resistance and lubricity, but to ensure its rust and corrosion resistance, the addition amount is required to be relatively high, and it needs to be compounded with tall oil imidazoline sulfonate, benzimidazole and triethanolamine. The addition amount of boric acid ester is reduced on the basis of ensuring the rust and corrosion resistance of the concentrated solution.

[0032] In the embodiment of the present invention, the formula of the concentrated liquid for hydraulic support is reasonably compounded so that it can still meet the technical requirements of the coal industry MT / T 76-2011 "Technical requirements for emulsified oil, concentrated liquid and high-water content hydraulic fluid for hydraulic support" in a high hard water (artificial hardness classification 40) system, and has good stability, anti-rust and anti-corrosion properties and hard water resistance; and has good biodegradability, which can reduce pollution to the environment.

[0033] In some embodiments, two or more borate esters are used, preferably two different borate esters, and the mass ratio of the two borate esters is 2:1.

[0034] In some embodiments, the borate is a compound of two or more of tall oil diethanolamide borate, oleic acid diethanolamide borate, triethanolamine borate, and stearic acid diethanolamide borate, and it cooperates with tall oil imidazoline sulfonate, benzimidazole, and triethanolamine to play an anti-rust and anti-corrosion role. The mass ratio of the borate to the imidazoline sulfonate, the benzotriazole, and the triethanolamine is (2-4): (1-3): (0.5-1): (1-3).

[0035] In some embodiments, tall oil imidazoline sulfonate is a new type of amphoteric surfactant, which is green, environmentally friendly and easily biodegradable; fatty alcohol polyoxyethylene ether carboxylate is a type of multifunctional anionic surfactant, in which the fatty alcohol group is preferably one of lauryl alcohol, decanol and octanol.

[0036] In some embodiments, the alkyl carboxylic acid isomeric polyol amine soap is a nonionic surfactant, which has good solubility in hard water systems and does not produce soap precipitation. In addition, the soap can be compounded with a multifunctional surfactant to enhance the lubrication and anti-rust properties of the concentrate.

[0037] In some embodiments, fatty alcohol polyoxyethylene ether carboxylate is a multifunctional anionic surfactant, alkyl carboxylic acid isomeric polyol amine soap is a nonionic surfactant, and if fatty alcohol polyoxyethylene ether carboxylate and alkyl carboxylic acid isomeric polyol amine soap are added, the mass ratio of the two is 2:1.

[0038] In some embodiments, the anti-hard water agent is a compound of two or more of sodium gluconate, tetrasodium glutamate diacetate and trisodium methylglycine diacetate.

[0039] Another aspect of the present invention is to provide a method for preparing the above-mentioned concentrated liquid for hydraulic support, the method comprising the following steps:

[0040] (1) adding boric acid ester, tall oil imidazoline sulfonate, benzimidazole and triethanolamine to water in proportion, heating and stirring to obtain a mixed solution;

[0041] (2) Adding a multifunctional surfactant and a nonionic surfactant to the mixed solution obtained in step (1) in proportion, and continuing to add an anti-hard water agent, heating and stirring, to obtain the concentrated solution for the fully biodegradable hydraulic support.

[0042] The preparation method of the concentrated liquid for hydraulic supports in the embodiment of the present invention has a simple process, simple production equipment, low raw material cost, mild reaction conditions, low energy consumption, and is suitable for large-scale industrial production. The prepared concentrated liquid for hydraulic supports has excellent anti-rust and anti-corrosion properties and outstanding lubrication properties, and the concentrated liquid has good biodegradability, reducing pollution to the environment.

[0043] In some embodiments, in step (1), the temperature of heating and stirring is 30-50° C., and the stirring time is 10-15 min.

[0044] In some embodiments, in step (2), the temperature of heating and stirring is 20 to 40° C., and the stirring time is 20 to 40 min.

[0045] The present invention is further described in detail below with reference to specific embodiments.

[0046] [Example 1]

[0047] A hydraulic support concentrate, wherein the components and mass percentage contents thereof are:

[0048]

[0049] Among them, the borate ester is a compound of tall oil acid diethanolamide borate, oleic acid diethanolamide borate and triethanolamide borate, and the mass ratio of the three is 1:1:2; the borate ester in the formula, tall oil imidazoline sulfonate, benzimidazole, and triethanolamine form a composite rust and corrosion inhibitor; and the borate ester, tall oil imidazoline sulfonate, benzimidazole, and triethanolamine are compounded in a mass ratio of 3:1:0.5:1.5.

[0050] Among them, the multifunctional anionic surfactant fatty alcohol polyoxyethylene ether carboxylic acid is lauryl alcohol polyoxyethylene ether carboxylic acid, the nonionic surfactant alkyl carboxylic acid isomeric polyol amine soap is tetradecyl carboxylic acid isomeric polyol amine soap, and lauryl alcohol polyoxyethylene ether carboxylic acid and tetradecyl carboxylic acid isomeric polyol amine soap are compounded in a mass ratio of 2:1.

[0051] Among them, the anti-hard water agent is a compound of sodium gluconate and tetrasodium glutamate diacetate, and the mass ratio of sodium gluconate to tetrasodium glutamate diacetate is 1:2.

[0052] The specific preparation method of the concentrated liquid for hydraulic support of this embodiment is as follows:

[0053] (1) According to the mass ratio of the components of the rust and corrosion inhibitor, boric acid ester, tall oil imidazoline sulfonate, benzimidazole and triethanolamine were added to water, and stirred at 40° C. for 10 minutes to obtain a mixed solution.

[0054] (2) Add lauryl alcohol polyoxyethylene ether carboxylic acid and tetradecyl carboxylic acid isomeric polyol amine soap in proportion to the mixed solution obtained in step (1), continue to add anti-hard water agent, keep stirring at 30° C. for 30 minutes to obtain the product.

[0055] [Example 2]

[0056] The boric acid ester in the formula of Example 1 is replaced with a combination of tall oil diethanolamide borate, oleic acid diethanolamide borate, and stearic acid diethanolamide borate in a mass ratio of 1:1:1. The other components, their respective proportions, and the preparation method are the same as those in Example 1.

[0057] [Example 3]

[0058] The boric acid ester in the formula of Example 1 was replaced with a compound of tall oil diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate in a mass ratio of 1:2:1. The other components and their respective proportions and preparation methods were the same as those in Example 1.

[0059] [Example 4]

[0060] The boric acid ester in the formula of Example 1 is replaced with oleic acid diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate in a mass ratio of 1:2:1. The other components and their respective proportions and preparation methods are the same as those in Example 1.

[0061] [Example 5]

[0062] A concentrated liquid for hydraulic support, the components and mass percentages of which are as follows:

[0063]

[0064] Among them, the borate ester is a compound of tall oil acid diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate, and the mass ratio of the three is 1:2:1; the borate ester in the formula and tall oil imidazoline sulfonate, benzimidazole, and triethanolamine form a composite rust and corrosion inhibitor; and the borate ester, tall oil imidazoline sulfonate, benzimidazole, and triethanolamine are compounded in a mass ratio of 4:0.5:0.25:1.

[0065] Among them, the multifunctional anionic surfactant fatty alcohol polyoxyethylene ether carboxylate is decanol polyoxyethylene ether carboxylate, the nonionic surfactant alkyl carboxylic acid isomeric polyol amine soap is octadecyl carboxylic acid isomeric polyol amine soap, and the decanol polyoxyethylene ether carboxylate and octadecyl carboxylic acid isomeric polyol amine soap are compounded in a mass ratio of 2:1.

[0066] Among them, the anti-hard water agent is a compound of sodium gluconate and trisodium methylglycine diacetate, and the mass ratio of sodium gluconate to trisodium methylglycine diacetate is 1:1.

[0067] The specific preparation method of the concentrated liquid for hydraulic support of this embodiment is as follows:

[0068] (1) adding boric acid ester, tall oil imidazoline sulfonate, benzimidazole and triethanolamine to water according to the mass ratio of the components of the rust and corrosion inhibitor, and stirring at 45° C. for 10 minutes to obtain a mixed solution;

[0069] (2) Adding decyl alcohol polyoxyethylene ether carboxylic acid and octadecyl carboxylic acid isomeric polyol amine soap in proportion to the mixed solution obtained in step (1), and continuing to add an anti-hard water agent, stirring at 35° C. for 30 minutes to obtain the mixture.

[0070] [Example 6]

[0071] The boric acid ester in the formula of Example 5 is replaced with a combination of tall oil diethanolamide borate, oleic acid diethanolamide borate and triethanolamide borate in a mass ratio of 1:1:2. The other components and their respective proportions and preparation methods are the same as those in Example 5.

[0072] [Example 7]

[0073] The boric acid ester in the formula of Example 5 is replaced with a compound of tall oil diethanolamide borate, oleic acid diethanolamide borate and stearic acid diethanolamide borate in a mass ratio of 1:1:1. The other components and their respective proportions and preparation methods are the same as those in Example 5.

[0074] [Example 8]

[0075] The boric acid ester in the formula of Example 5 is replaced with a compound of oleic acid diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate, and the mass ratio of the three is 1:2:1. The other components and their respective proportions and preparation methods are the same as those in Example 5.

[0076] [Example 9]

[0077] A concentrated liquid for hydraulic support, the components and mass percentages of which are as follows:

[0078]

[0079] Alkyl carboxylic acid isomeric polyol amine soap 1%

[0080] Anti-hard water agent 2%

[0081] Water (tap water) 81.5%

[0082] Among them, the borate ester is a compound of oleic acid diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate, and the mass ratio of the three is 1::2:1; the borate ester in the formula and tall oil imidazoline sulfonate, benzimidazole, and triethanolamine form a composite rust and corrosion inhibitor; and the borate ester, tall oil imidazoline sulfonate, benzimidazole, and triethanolamine are compounded in a mass ratio of 2:1.5:0.75:2.5.

[0083] Among them, the multifunctional anionic surfactant fatty alcohol polyoxyethylene ether carboxylate is octanol polyoxyethylene ether carboxylic acid, the nonionic surfactant alkyl carboxylic acid isomeric polyol amine soap is dodecyl carboxylic acid isomeric polyol amine soap, and octanol polyoxyethylene ether carboxylic acid and dodecyl carboxylic acid isomeric polyol amine soap are compounded in a mass ratio of 2:1.

[0084] Among them, the anti-hard water agent is a compound of tetrasodium glutamate diacetate and trisodium methylglycine diacetate, and the mass ratio of tetrasodium glutamate diacetate and trisodium methylglycine diacetate is 1:1.

[0085] The specific preparation method of the concentrated liquid for hydraulic support of this embodiment is as follows:

[0086] (1) adding borate, tall oil imidazoline sulfonate, benzimidazole and triethanolamine to water according to the mass ratio of the components of the rust and corrosion inhibitor, and stirring at 40° C. for 10 minutes to obtain a mixed solution;

[0087] (2) Add octanol polyoxyethylene ether carboxylic acid and dodecyl carboxylic acid isomeric polyol amine soap in proportion to the mixed solution obtained in step (1), continue to add anti-hard water agent, keep stirring at 30° C. for 30 minutes to obtain the product.

[0088] [Example 10]

[0089] The boric acid ester in the formula of Example 9 is replaced with a compound of tall oil diethanolamide borate, oleic acid diethanolamide borate and triethanolamide borate in a mass ratio of 1:1:2. The other components and their respective proportions and preparation methods are the same as those in Example 9.

[0090] [Example 11]

[0091] The boric acid ester in the formula of Example 9 is replaced with a combination of tall oil diethanolamide borate, oleic acid diethanolamide borate and stearic acid diethanolamide borate in a mass ratio of 1:1:1. The other components and their respective proportions and preparation methods are the same as those in Example 9.

[0092] [Example 12]

[0093] The boric acid ester in the formula of Example 9 is replaced with a compound of tall oil acid diethanolamide borate, triethanolamide borate and stearic acid diethanolamide borate, and the mass ratio of the three is 1:2:1. The other components and their respective proportions and preparation methods are the same as those in Example 9.

[0094] [Comparative Example 1]

[0095] The mass ratio of borate ester, tall oil imidazoline sulfonate, benzimidazole and triethanolamine in the formula of Example 1 is 3:1:0.5:1.5, and the same mass of borate ester is used. The other components and their respective proportions and preparation methods are the same as those in Example 1. The mass percentage content of each component is:

[0096]

[0097] [Comparative Example 2]

[0098] The borate content in the formula of comparative example 1 was increased to 20%, and the other components and their respective proportions and preparation methods were the same as those of comparative example 1. The mass percentage content of each component was:

[0099]

[0100] According to the coal industry standard MT76-2011 "Technical requirements for emulsified oil, concentrate and high water content hydraulic fluid for hydraulic supports", the performance test of the concentrated liquid for hydraulic supports prepared in Examples 1 to 12 was carried out, and the results showed that they all met the technical requirements specified in the standard. Taking Example 1 as an example, its test results are compared in detail with the technical requirements of the coal industry standard MT 76-2011, and the test results of the other examples are not repeated here. The hardness of the artificial hard water prepared in this test is 2000ppm, and the test results are shown in Table 1.

[0101] Table 1

[0102]

[0103]

[0104] The following is an example of the performance test of the concentrated liquid for hydraulic supports of Examples 5 and 9 and Comparative Examples 1-2 to illustrate the performance of the concentrated liquid for hydraulic supports obtained in the embodiments of the present invention. The test method and requirements are exactly the same as those in Example 1, that is, the correlation test is performed according to the technical requirements of the coal industry standard MT76-2011, and the test results are shown in Table 2 below.

[0105] Table 2

[0106]

[0107]

[0108] Combining Table 1 and Table 2, it can be seen that in Examples 5 and 9, when the mass proportion of boric acid ester in the rust and corrosion inhibitor increases, the maximum non-seizure composite P B The value increases, and the lubrication performance of the concentrated liquid for hydraulic support is improved. The lubrication performance of the three embodiments is far higher than the technical standard 392N of the coal industry, and the anti-rust and anti-corrosion performance meets the industry standard; in comparative example 1, when no tall oil imidazoline sulfonate, benzimidazole, and triethanolamine are added to the components, and the three components are replaced by boric acid esters, the anti-rust and anti-corrosion performance of the concentrated liquid for hydraulic support is reduced, but with the increase of the boric acid ester content, its lubrication performance is greatly improved; in comparative example 2, when the boric acid ester content is increased to 20% on the basis of comparative example 1, its anti-rust and anti-corrosion performance and lubrication performance meet the industry standard. It can be seen that on the basis of ensuring the anti-rust and anti-corrosion performance of the concentrated liquid, the addition of tall oil imidazoline sulfonate, benzimidazole and triethanolamine in the formula reduces the amount of boric acid ester added and reduces the cost.

[0109] In summary, the concentrated liquid for hydraulic supports prepared according to the proportion of components in the formula of the present invention has excellent properties such as good anti-rust and anti-corrosion performance, lubrication performance, stability, and hard water resistance, and the cost is lower than that of other embodiments. At the same time, it is highly biodegradable, environmentally friendly, and conducive to sustainable development.

[0110] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, any modification and improvement made to the technical solution of the present invention by a person skilled in the art shall fall within the protection scope of the claims of the present invention.

Claims

1. A concentrated liquid for high hardness water resistant hydraulic support, characterized in that: It is composed of the following components in percentage by mass: The preparation process of the concentrated liquid for high-hardness water resistant hydraulic support comprises the following steps: (1) adding boric acid ester, tall oil imidazoline sulfonate, benzimidazole and triethanolamine to water in proportion, heating and stirring to obtain a mixed solution; (2) Adding fatty alcohol polyoxyethylene ether carboxylic acid, alkyl carboxylic acid isomeric polyol amine soap and anti-hard water agent to the mixed solution obtained in step (1), heating for reaction, and obtaining a concentrated solution for high-hard water resistant hydraulic support.

2. The concentrated liquid for high hardness water resistant hydraulic support according to claim 1, characterized in that: In the component composition of the concentrated liquid for hydraulic support, the weight ratio of the boric acid ester to tall oil imidazoline sulfonate, benzimidazole and triethanolamine is (2-4): (1-3): (0.5-1): (1-3).

3. The concentrated liquid for high hardness water resistant hydraulic support according to claim 1, characterized in that: The borate is a mixture of two or more of tall oil diethanolamide borate, oleic acid diethanolamide borate, triethanolamide borate, and stearic acid diethanolamide borate.

4. The concentrated liquid for high hardness water resistant hydraulic support according to claim 1, characterized in that: The anti-hard water agent is a compound of two or more of sodium gluconate, tetrasodium glutamate diacetate and trisodium methylglycine diacetate.

5. The concentrated liquid for high hardness water resistant hydraulic support according to claim 4, characterized in that: The anti-hard water agent is a compound of two of sodium gluconate, tetrasodium glutamate diacetate and trisodium methylglycine diacetate, and the mass ratio of the two anti-hard water agents is (1-2):

1.

6. The concentrated liquid for high hardness water resistant hydraulic support according to claim 1, characterized in that: The fatty alcohol polyoxyethylene ether carboxylate is one of lauryl alcohol polyoxyethylene ether carboxylate, decanol polyoxyethylene ether carboxylate and octanol polyoxyethylene ether carboxylate.

7. The concentrated liquid for high hardness water resistant hydraulic support according to claim 1, characterized in that: The alkyl carboxylic acid isomeric polyol amine soap is any one of dodecyl carboxylic acid isomeric polyol amine soap, tetradecyl carboxylic acid isomeric polyol amine soap, and octadecyl carboxylic acid isomeric polyol amine soap.

8. The concentrated liquid for high hardness water resistant hydraulic support according to any one of claims 1 to 7, characterized in that: In step (1), the heating and stirring temperature is 30 to 50° C., and the stirring time is 10 to 15 minutes.

9. The concentrated liquid for high hardness water resistant hydraulic support according to any one of claims 1 to 7, characterized in that: In step (2), the heating and stirring reaction temperature is 20 to 40° C., and the stirring reaction time is 20 to 40 min.

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