Concentrated solution for hydraulic support as well as preparation method and application of concentrated solution

Abstract

The invention discloses a concentrated solution for a hydraulic support, and belongs to a transmission medium for a coal mine hydraulic support. The lubricating oil comprises the following components in percentage by mass: 2-5% of a lubricating complexing agent, 6-10% of an anti-rust complexing agent, 0.2-1.5% of a complexing complexing agent, 0.02-0.1% of a defoaming agent and the balance of water, the lubricating complexing agent comprises fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds. The technical problem that in the prior art, due to the fact that the dosage of each functional single agent of the concentrated solution is too high, the biological environmental protection performance is poor is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of transmission media for coal mine hydraulic supports, and particularly relates to a concentrated liquid for hydraulic supports, a preparation method thereof, and an application thereof. Background Art

[0002] The concentrated liquid for hydraulic supports is mainly used as a power transmission medium for systems such as coal mine single hydraulic props and hydraulic electric furnaces, and can effectively protect the hydraulic system and extend its service life. It is an important component of the hydraulic support. Its cooperation with the safety valve ensures the support effect of the hydraulic support, enables the constant resistance operation of the hydraulic support, and plays an important protective role in the safe operation of the hydraulic support. Therefore, the concentrated liquid for hydraulic supports is also a key link in safe production.

[0003] The concentrated liquid for hydraulic supports generally needs to be diluted with mine water. However, mine water generally contains calcium and magnesium ions, while traditional concentrated liquids for hydraulic supports generally contain soap-based lubricants. When the soap-based lubricants are mixed with mine water, a soap precipitation phenomenon will occur. Specifically, the hydraulic support emulsion oil uses base oil as a carrier. Since traditional emulsion oil belongs to a thermodynamically unstable system, its stability varies with the change of the use environment temperature, and there is still a certain amount of oil soap precipitation during use, causing the filter screen to be blocked and requiring frequent cleaning of the filter screen. And these precipitated oil soaps combine with coal dust to form a sticky substance that is difficult to clean, usually causing many troubles in on-site use. And for the electro-hydraulic control system, it will block its filtering components. In addition, due to the large number of sealing points of various pipeline joints, the high-water-content hydraulic fluid prepared from emulsion oil or concentrated liquid leaks more during use. The mineral oil in the hydraulic support emulsion oil has relatively stable performance and becomes the main pollution component, polluting the environment, especially polluting the underground water resources. In the prior art, in order to prevent the occurrence of soap precipitation, the concentrated liquid for hydraulic supports needs to be compounded with a certain proportion of chelating agents such as EDTA (sodium ethylenediaminetetraacetate) according to the hardness of the mine water to complex and remove the calcium and magnesium ions in the mine water. EDTA is non-toxic and non-irritating, but due to the stable nature and strong coordination ability of the chelating agent, it will not only increase the solubility of heavy metals, causing the accumulation of heavy metals in water, but also because of its excellent stability, it is very difficult to be biodegradable, causing water pollution and great harm.

[0004] In addition, there are significant differences and large variations in the water salinity of mining areas in China, which makes it difficult to match the concentrate types with the water quality. It is very hard for the concentrate products of the same type to fully adapt to the mine water within the corresponding hardness range. In the same mining area, different water sources are used with the change of fully mechanized mining faces, which will cause changes in the water quality for preparing the liquid, thus making it not match the product type and affecting the performance. On the one hand, the continuous change of mine water quality easily leads to the mismatch between mine water and product type, affecting the performance. If not discovered in time, it will cause economic losses and even potential safety hazards. On the other hand, if the product type is continuously changed to adapt to the mine water quality, it will also increase the management difficulty and cost of coal mining enterprises.

[0005] Chinese Patent has disclosed a concentrate for hydraulic supports with anti-hard water and low COD and its preparation method. Although this patent has solved the problem that the concentrate for hydraulic supports is prone to react with mine water in high-water-content hydraulic fluids, resulting in soap precipitation, blockage of the hydraulic system, and serious pollution, in this concentrate, the dosage of various functional single agents is very high, causing great pollution to the mine water source and making it not have good bio-environmental protection performance. Summary of the Invention

[0006] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a concentrate for hydraulic supports, its preparation method and application, so as to solve the technical problem that the high dosage of various functional single agents in the existing concentrate leads to poor bio-environmental protection performance.

[0007] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0008] The present invention provides a concentrate for hydraulic supports, including the following components, by mass percentage:

[0009] Lubricating compound: 2% - 5%

[0010] Rust-proof compound: 6% - 10%

[0011] Complexing compound: 0.2% - 1.5%

[0012] Defoamer: 0.02% - 0.1%

[0013] Water: the balance;

[0014] The lubricating compound includes fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds.

[0015] Preferably, the polyoxyethylene ether carboxylic acid compounds include one or a combination of two of castor oil polyoxyethylene ether carboxylic acid or fatty alcohol polyoxyethylene ether carboxylic acid.

[0016] More preferably, the mass ratio of the castor oil polyoxyethylene ether carboxylic acid to the fatty alcohol polyoxyethylene ether carboxylic acid is (1 - 2):1.

[0017] More preferably, the fatty alcohol polyoxyethylene ether carboxylic acid includes fatty primary alcohol polyoxyethylene ether carboxylic acid, which has more excellent lubricating performance and biodegradability, and helps to improve the lubricating effect and environmental protection performance of the concentrate.

[0018] Preferably, the rust prevention compound is prepared by mixing a carboxylic acid and an alkanolamine, followed by heating, stirring and cooling; the mass ratio of the carboxylic acid to the alkanolamine is 1:(1 - 2).

[0019] Preferably, the carboxylic acid includes a combination of two or more of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.

[0020] Preferably, the organic alkanolamine includes one or a combination of two of monoethanolamine, diethanolamine or triethanolamine.

[0021] Preferably, the complexing compound includes a combination of two or more of polyaspartic acid, tetrasodium glutamate diacetate or trisodium methylglycine diacetate.

[0022] Preferably, the defoaming agent includes a modified polysiloxane defoaming agent.

[0023] The present invention also provides a preparation method of the above-mentioned concentrate for hydraulic supports, which includes sequentially adding water and a complexing agent in proportion, stirring, then adding a lubricating compound and a rust prevention compound and continuing to stir, and finally adding a defoaming agent and stirring to obtain the concentrate for hydraulic supports.

[0024] Preferably, the above-mentioned stirring time is 40 - 120 min.

[0025] More preferably, the preparation method of the fatty alcohol amide polyoxyethylene ether includes: heating the fatty acid alkanolamide to 100 - 140 °C, introducing ethylene oxide and reacting for 2 - 3 h to obtain the fatty alcohol amide polyoxyethylene ether; the molar ratio of the fatty acid alkanolamide to ethylene oxide is 1:(4 - 6).

[0026] In the preparation method of fatty alcohol amide polyoxyethylene ether, firstly, fatty acid organic alcohol amide itself has lubricity and surface activity, which is an important basis for preparing high-performance surfactants. Ethylene oxide is selected as the polymerization monomer and reacts with fatty acid organic alcohol amide to form a polyoxyethylene chain, increasing the hydrophilicity and flexibility of the molecule, thereby improving the water solubility and lubricating performance of the lubricating compound. 100 - 140 °C is a suitable temperature range, which can not only ensure the reaction rate but also avoid side reactions caused by too high temperature; secondly, a reaction time of 2 - 3 hours is sufficient for ethylene oxide to fully polymerize onto the fatty acid organic alcohol amide molecule to form stable fatty alcohol amide polyoxyethylene ether; finally, the molar ratio of fatty acid organic alcohol amide to ethylene oxide is 1:(4 - 6), and this ratio ensures that the length of the polyoxyethylene chain is appropriate, neither too long resulting in a decrease in water solubility nor too short affecting the lubricating performance;

[0027] Further preferably, the preparation method of the fatty acid organic alcohol amide includes: mixing fatty acid and organic alcohol amine in a mass ratio of 1:1 to obtain mixture A, and then adding an alkaline catalyst. The mass ratio of mixture A to the alkaline catalyst is 1:(0.002 - 0.01). Heat to 160 °C and stir. After reacting for 3 - 4 h, cool to 100 - 105 °C and continue to react for 2 - 3 h to obtain fatty acid organic alcohol amide.

[0028] Further preferably, in the preparation method of the fatty acid organic alcohol amide, 3 / 4 of the organic alcohol amine is added before heating to react the organic alcohol amine with the fatty acid to form amide, and the remaining 1 / 4 of the organic alcohol amine is added after cooling to react the organic alcohol amine to form alcohol amide.

[0029] Further preferably, the fatty acid includes one or more of oleic acid, castor oil or rapeseed oil.

[0030] Further preferably, the organic alcohol amine includes one or a combination of two of monoethanolamine, diethanolamine or triethanolamine.

[0031] Further preferably, the alkaline catalyst includes sodium hydroxide or potassium hydroxide.

[0032] Further preferably, the preparation method of the polyoxyethylene ether carboxylic acid compound includes: mixing the polyoxyethylene ether carboxylic acid compound and oleic acid in a mass ratio of 1:(0.5 - 1) to obtain mixture B, and then adding boric acid. The mass ratio of mixture B to boric acid is 1:(0.002 - 0.005). Heat to 130 °C - 150 °C and stir for 1.5 - 5.5 h, and then cool to obtain the polyoxyethylene ether carboxylic acid compound.

[0033] In the preparation method of fatty alcohol polyoxyethylene ether carboxylic acid, first, a polyoxyethylene ether carboxylic acid compound is selected as the starting material. Because it has hydrophilicity and surface activity itself, it is easy to undergo a condensation reaction with oleic acid, making the reactant have the common advantages of fatty alcohol polyoxyethylene ether and oleic acid, that is, it has good water solubility and good lubricity. Boric acid is selected as the catalyst to promote the reaction, improve the reaction efficiency and product purity; secondly, 130°C - 150°C is a suitable temperature range, which can not only ensure the reaction rate but also avoid side reactions and product decomposition caused by too high temperature. The stirring time of 1.5 - 5.5 hours ensures that the reaction proceeds fully to form a stable fatty alcohol polyoxyethylene ether carboxylic acid; finally, the mass ratio of mixture B to boric acid of 1:(0.002 - 0.005) ensures the smooth progress of the reaction and the quality of the product.

[0034] Further preferably, the polyoxyethylene ether carboxylic acid compound includes one or a combination of two of castor oil polyoxyethylene ether carboxylic acid or fatty alcohol polyoxyethylene ether carboxylic acid.

[0035] Further preferably, the mass ratio of castor oil polyoxyethylene ether carboxylic acid to fatty alcohol polyoxyethylene ether carboxylic acid is (1 - 2):1.

[0036] Further preferably, the preparation method of the rust prevention compound includes: mixing carboxylic acid and alkanolamine in a mass ratio of 1:(1 - 2), heating and stirring at 65 - 75°C for 1 - 4 h to form a light yellow transparent liquid, and obtaining the rust prevention compound after cooling.

[0037] By selecting appropriate carboxylic acid and alkanolamine, as well as reasonable ratio and reaction conditions, a rust prevention compound with good rust prevention performance and stability is prepared. This method provides a technical reference for the preparation of high - efficiency and environmentally friendly rust preventives.

[0038] The present invention also provides the application of the above - mentioned concentrate in the field of transmission media for hydraulic supports.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The present invention provides a concentrated liquid for hydraulic supports. By using fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds as lubricating complex agents, these lubricants contain abundant polar groups, which are easy to adsorb on the metal surface to form a protective film, playing an effective lubricating role and a certain rust-proof role. The present invention effectively combines the lubricating complex agent and the rust-proof complex agent. When the total dosage of the two is maintained at 8%-15% (the content of the lubricating complex agent and the rust-proof lubricant in the high-water-content hydraulic fluid is 0.4%-0.75%), good lubricating and rust-proof properties can still be ensured. At the same time, the dosage of various functional single agents is effectively reduced, the chemical oxygen demand (COD) value is effectively reduced, the pollution of mine water sources is reduced, and the biological environmental protection of the concentrated liquid is improved. Even if there is leakage during use, it will not cause harm to the environment. Fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds belong to green surfactants with nonionic-anionic structures. From the molecular structure, these two substances have ether bonds, amide bonds, etc. different from ordinary surfactants, thus integrating the characteristics of these two types of surfactants, namely anionic and nonionic surfactants. The ethoxy groups in fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds can greatly increase the volume of the polar head, preventing to a certain extent the combination of the positive ion polar head and the negative ion polar head from being too tight to form precipitation, so that the concentrated liquid has better water solubility, hard water resistance and calcium soap dispersion ability than ordinary anionic surfactants. The lubricating complex agent of the present invention combines many advantages of the above two surfactants, can stably exist in the electrolyte solution, is not easily precipitated at high temperature, and avoids the occurrence of soap precipitation in the concentrated liquid due to Ca 2+ and Mg 2+ in the mine mixing water. At the same time, all the various functional single agents selected in the present invention are low-foaming additives, reducing the addition of defoamers in the formula, effectively preventing the precipitation of defoamers during storage, and thus making the formula system more stable.

[0041] Furthermore, castor oil polyoxyethylene ether carboxylic acid has good lubricating properties, which can effectively reduce the friction and wear between the moving parts of the hydraulic support, extend the service life of the equipment, and can be evenly dispersed in the concentrate to ensure the full mixing of each component, improving the stability and uniformity of the concentrate; fatty alcohol polyoxyethylene ether carboxylic acid has excellent emulsifying properties, which can mix immiscible liquids such as oil and water together to form a stable emulsion, contributing to cleaning and lubrication. This compound can quickly wet various surfaces, improving the spreading and permeability of the concentrate on the surface of the hydraulic support; the mixture prepared by adjusting the ratio of castor oil polyoxyethylene ether carboxylic acid and fatty alcohol polyoxyethylene ether carboxylic acid can optimize the lubricating properties, emulsifying properties, and wettability of the concentrate. These two compounds produce a synergistic effect in the concentrate, further improving the efficacy and stability of the concentrate. The use of the mixture enables the concentrate to be applicable to a wider range of hydraulic supports and equipment, improving its versatility and applicability.

[0042] Furthermore, the rust preventive compound uses an organic carboxylic acid rust preventive, which is prepared by mixing carboxylic acid and alkanolamine. It has good rust prevention properties and certain lubricity, and is also easily biodegradable, reducing the harm to the environment. At the same time, the rust preventive of the present invention has good antibacterial properties, and good antibacterial effects can be ensured without adding additional antibacterial agents, so that the concentrate has certain antibacterial properties. It has been experimentally verified that the concentrate of the present invention has not shown mildew after being placed at room temperature for 2 months.

[0043] Furthermore, monocarboxylic acid has certain cleaning ability, which can remove dirt and impurities in the hydraulic system, keeping the system clean and unobstructed; the two carboxyl groups in dicarboxylic acid can undergo complexation reactions with hardness ions in water (such as calcium and magnesium ions), preventing these ions from forming precipitates and scale in the hydraulic system, keeping the system clean and operating efficiently; with the increase in the number of carboxyl groups, tricarboxylic acid and tetracarboxylic acid may have more excellent rust prevention and complexation properties, and they can form more stable and complex protective films and complexes, providing more comprehensive protection for the hydraulic system.

[0044] Furthermore, the alkanolamine is selected from one or two of monoethanolamine, diethanolamine, and triethanolamine, realizing the synergistic effect of various carboxylic acids, improving the rust prevention ability and application range of the rust preventive. At the same time, the addition of alkanolamine also enhances the stability and solubility of the rust preventive compound. These alkanolamines have good reaction activity and rust prevention properties, contributing to further improving the effect of the rust preventive compound.

[0045] Furthermore, a complexing agent composed of two or more of polyaspartic acid, disodium glutamate diacetate, and trisodium methylglycine diacetate enhances the complexing ability of the concentrate, helps remove impurities and deposits in the hydraulic system, and improves the cleanliness and operating efficiency of the system. In addition, the concentrate of the present invention does not contain an EDTA complexing agent, and an amino acid-based complexing agent that is easily biodegradable is selected, further improving the environmental performance of the product.

[0046] Furthermore, the modified polysiloxane defoaming agent has efficient defoaming and foam suppression properties, which helps maintain the stability and reliability of the hydraulic system and avoid operating failures caused by foam generation.

[0047] The present invention also provides a preparation method of the above-mentioned concentrate for hydraulic supports. By sequentially adding each component in proportion and stirring evenly, a concentrate for hydraulic supports with excellent performance can be prepared. This method has the advantages of simple process, easy control, and stable product performance. Detailed implementation manners

[0048] To enable those skilled in the art to understand the features and effects of the present invention, the following provides only a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art for the present invention. In case of conflict, the definition in this specification shall prevail.

[0049] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0050] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0051] In this article, unless otherwise specified, terms such as "comprise", "include", "contain", "have", or similar terms cover the meanings of "consist of" and "consist essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A consists only of a".

[0052] In this article, for the sake of concise description, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as the scope described in this specification.

[0053] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0054] Conventional instrument equipment in the art is used in the following embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following embodiments. Unless otherwise stated, commercially available products are used, and their specifications are the conventional specifications in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0055] The present invention is used to prepare the concentrate for general-purpose environmental protection hydraulic supports, and the performance indicators are tested according to the MT76 standard. At the same time, the chemical oxygen demand CODcr value is determined according to HJ / T 399-2007 "Determination of Chemical Oxygen Demand in Water Quality" as an index to measure environmental protection.

[0056] Example 1

[0057] 1) Preparation of lubricating compound (fatty alcohol amide polyoxyethylene ether): Oleic acid and monoethanolamine are mixed in a mass ratio of 1:1 to obtain mixture A, and then sodium hydroxide is added. The mass ratio of mixture A to sodium hydroxide is 1:0.002. Heat to 160°C and stir. After reacting for 3 h, cool to 100°C and continue to react for 2 h to obtain fatty acid organic alcohol amide. Among them, the addition amount of organic alcohol amine before heating is 3 / 4, and the remaining 1 / 4 of organic alcohol amine is added after cooling; Heat the fatty acid organic alcohol amide to 100°C and introduce ethylene oxide to react for 2 h to obtain fatty alcohol amide polyoxyethylene ether; The molar ratio of the fatty acid organic alcohol amide to ethylene oxide is 1:4;

[0058] 2) Preparation of rust prevention compound: Monocarboxylic acid and tricarboxylic acid are mixed in a mass ratio of 1:1 to obtain mixture C. Mixture C and monoethanolamine are mixed in a volume ratio of 1:1, heated and stirred at 65°C for 2 h to form a light yellow transparent liquid, and the rust prevention compound is obtained after cooling;

[0059] 3) Preparation of complexing compound: Polyaspartic acid and sodium glutamate diacetate are mixed in a mass ratio of 1:2;

[0060] 4) Add water: 87.45%, complexing agent mixture: 0.5% in sequence. After stirring, add lubricating complexing agent: 2%, rust preventive complexing agent: 10%, and continue stirring; finally, add defoaming agent 0.05% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 40 min.

[0061] Example 2

[0062] 1) Prepare lubricating complexing agent (fatty alcohol amide polyoxyethylene ether): Mix castor oil and diethanolamine in a mass ratio of 1:1 to obtain mixture A, then add potassium hydroxide, and the mass ratio of mixture A to potassium hydroxide is 1:0.006. Heat to 160 °C and stir. After reacting for 4 h, cool to 105 °C and continue reacting for 3 h to obtain fatty acid organic alcohol amide; among them, the addition amount of organic alcohol amine before heating is 3 / 4, and the remaining 1 / 4 of organic alcohol amine is added after cooling. Heat the fatty acid organic alcohol amide to 140 °C and introduce ethylene oxide to react for 3 h to obtain fatty alcohol amide polyoxyethylene ether; the molar ratio of fatty acid organic alcohol amide to ethylene oxide is 1:6;

[0063] 2) Prepare rust preventive complexing agent: Mix dibasic carboxylic acid and tribasic carboxylic acid in a mass ratio of 1.5:1 to obtain mixture C, mix mixture C and diethanolamine in a volume ratio of 1:1.5, heat and stir at 70 °C for 2 h to form a light yellow transparent liquid, and obtain the rust preventive complexing agent after cooling;

[0064] 3) Prepare complexing agent mixture: Mix tetrasodium glutamate diacetate and trisodium methylglycine diacetate in a mass ratio of 1:1;

[0065] 4) Add water: 88.98%, complexing agent mixture: 1% in sequence. After stirring, add lubricating complexing agent: 3%, rust preventive complexing agent: 7%, and continue stirring; finally, add defoaming agent 0.02% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 60 min.

[0066] Example 3

[0067] 1) Prepare lubricating complexing agent (castor oil polyoxyethylene ether carboxylic acid): Mix castor oil polyoxyethylene ether and oleic acid in a mass ratio of 1:0.5 to obtain mixture B, add boric acid, and the mass ratio of mixture B to boric acid is 1:0.002. Heat to 130 °C and stir for 1.5 h, and obtain castor oil polyoxyethylene ether carboxylic acid after cooling;

[0068] 2) Preparation of rust preventive compound: Mix monocarboxylic acid, dicarboxylic acid or tricarboxylic acid in a mass ratio of 0.5:0.5:1 to obtain mixture C. Mix monoethanolamine and diethanolamine in a mass ratio of 1:1 to obtain mixture D. Mix mixture C and mixture D in a volume ratio of 1:2, heat and stir at 75°C for 2 h to form a light yellow transparent liquid, and obtain the rust preventive compound after cooling.

[0069] 3) Preparation of complexing compound: Mix polyaspartic acid, tetrasodium glutamate diacetate and trisodium methylglycine diacetate in a mass ratio of 0.5:0.5:1.

[0070] 4) Add water: 90.45%, complexing agent compound: 0.5% in sequence, stir and then add lubricating compound: 3%, rust preventive compound: 6%, and continue stirring; finally add antifoaming agent 0.05% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 80 min.

[0071] Example 4

[0072] 1) Preparation of lubricating compound (fatty alcohol amide polyoxyethylene ether): Mix rapeseed oil and triethanolamine in a mass ratio of 1:1 to obtain mixture A, then add sodium hydroxide agent, and the mass ratio of mixture A to sodium hydroxide is 1:0.01. Heat to 160°C and stir, after reacting for 3.5 h, cool to 103°C and continue reacting for 2.5 h to obtain fatty acid organic alcohol amide; among them, the addition amount of organic alcohol amine before heating is 3 / 4, and the remaining 1 / 4 of organic alcohol amine is added after cooling. Heat the fatty acid organic alcohol amide to 120°C and introduce ethylene oxide to react for 2.5 h to obtain fatty alcohol amide polyoxyethylene ether; the molar ratio of fatty acid organic alcohol amide to ethylene oxide is 1:5.

[0073] 2) Preparation of rust preventive compound: Mix tricarboxylic acid and tetracarboxylic acid in a mass ratio of 1:1 to obtain mixture C. Mix mixture C and triethanolamine in a volume ratio of 1:1, heat and stir at 65°C for 2 h to form a light yellow transparent liquid, and obtain the rust preventive compound after cooling.

[0074] 3) Preparation of complexing compound: Mix polyaspartic acid and tetrasodium glutamate diacetate in a mass ratio of 0.5:1.

[0075] 4) Add water: 87.45%, complexing agent compound: 0.5% in sequence, stir and then add lubricating compound: 5%, rust preventive compound: 7%, and continue stirring; finally add antifoaming agent 0.1% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 100 min.

[0076] Example 5

[0077] 1) Preparation of lubricating compound (fatty alcohol polyoxyethylene ether carboxylic acid): Mix fatty alcohol polyoxyethylene ether and oleic acid in a mass ratio of 1:1 to obtain mixture B, add boric acid, and the mass ratio of mixture B to boric acid is 1:0.005. Heat to 150 °C and stir for 5.5 h, and then obtain fatty alcohol polyoxyethylene ether carboxylic acid after cooling;

[0078] 2) Preparation of rust inhibitor compound: Mix monocarboxylic acid, dicarboxylic acid or tricarboxylic acid in a mass ratio of 1:0.5:1 to obtain mixture C, mix triethanolamine and diethanolamine in a mass ratio of 0.5:1 to obtain mixture D, mix mixture C and mixture D in a volume ratio of 1:2, heat and stir at 75 °C for 2 h to form a light yellow transparent liquid, and then obtain the rust inhibitor compound after cooling;

[0079] 3) Preparation of complexing compound: Mix polyaspartic acid, sodium glutamate diacetate and trisodium methylglycine diacetate in a mass ratio of 0.5:0.5:1;

[0080] 4) Add water: 88.45%, complexing agent compound: 0.5% in sequence, stir and then add lubricating compound: 4%, rust inhibitor compound: 7%, and continue to stir; finally add defoaming agent 0.05% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 110 min.

[0081] Example 6

[0082] 1) Preparation of lubricating compound (mixture of castor oil polyoxyethylene ether and fatty alcohol polyoxyethylene ether): Mix castor oil polyoxyethylene ether and fatty alcohol polyoxyethylene ether in a mass ratio of 1:1 to obtain mixture 3, mix mixture 3 and oleic acid in a mass ratio of 1:1 to obtain mixture B, add boric acid, and the mass ratio of mixture B to boric acid is 1:0.007. Heat to 140 °C and stir for 3.5 h, and then obtain mixture A after cooling;

[0083] 2) Preparation of rust inhibitor compound: Mix monocarboxylic acid, dicarboxylic acid or tricarboxylic acid in a mass ratio of 1:0.5:1 to obtain mixture C, mix triethanolamine and diethanolamine in a mass ratio of 0.5:1 to obtain mixture D, mix mixture C and mixture D in a volume ratio of 1:2, heat and stir at 75 °C for 2 h to form a light yellow transparent liquid, and then obtain the rust inhibitor compound after cooling;

[0084] 3) Preparation of complexing compound: Mix polyaspartic acid, sodium glutamate diacetate and trisodium methylglycine diacetate in a mass ratio of 0.5:0.5:1;

[0085] 4) Add water: 88.45%, complexing agent composite: 0.5% in sequence. After stirring, add lubricating composite: 4%, rust preventive composite: 7%, and continue stirring; finally, add defoaming agent 0.05% and stir to obtain the general-purpose environmentally friendly hydraulic support concentrate; the stirring time is 120 min.

[0086] Comparative Example 1

[0087] The difference between this Comparative Example 1 and Example 1 is that the preparation methods of the lubricating composite and the complexing composite in the concentrate of this Comparative Example 1 are different, and the other conditions are the same.

[0088] The preparation method of the lubricating composite in this Comparative Example 1 is prepared by using the preparation method of fatty soap lubricants and emulsifiers in "Research on New Synthetic Hydraulic Support Concentrates" by Xu Haixia, Wang Yimin, Yao Yuanshu, and Han Yong, Coal Journal, Vol. 29, No. 4, 2004, and specifically includes:

[0089] (1) Synthesis of lubricant: Synthesize the oily substance that can provide lubricating properties with the hydrophilic substance to make it a lubricant with hydrophilic functional groups. The preparation process: ① Heat vegetable oil A to 80 °C, add amine compounds and mix and stir in an appropriate ratio, and heat up to 130 - 140 °C for the synthesis reaction. The product is a viscous liquid, which has lubricity, good hydrophilicity, and is also a very effective black metal rust preventive. ② Vegetable oil B and water react under the action of sulfuric acid to generate unsaturated fatty acids and polyols, and stand to separate the polyols: Unsaturated fatty acids and polyols react under the action of sulfuric acid to generate unsaturated fatty acid esters and water: The unsaturated fatty acid esters are sulfonated, and the lower-layer waste acid is separated by standing (the waste acid must be neutralized with alkali): Neutralize the product to pH = 7.0 - 7.5. ③ Stir vegetable oil C, alkaline compound and water, and heat up to 95 °C for a chemical reaction, control the pH value during the reaction process, and the pH value is 9 at the end of the reaction;

[0090] (2) The purpose of solubilization of the composite emulsifier is to increase the dissolution degree of various additives in the concentrate and the dilution, and it has excellent stability. In the single-state solubilization model, the molecules of the solubilizate are between the "fences" of the micelles, that is, the non-polar hydrocarbon chains insert into the interior of the micelles, and the polar heads are between the polar groups of the surfactant and are connected by hydrogen bonds or dipole-dipole interactions. When the hydrocarbon chain of the polar organic matter is larger, the degree of insertion of the polar molecule into the micelle increases, and even the polar group is pulled into the micelle. For the non-ionic surfactant with polyoxyethylene groups, the solubilization method is that the solubilizate is included in the hydrophilic chain of the polyoxyethylene on the outer layer of the micelle. Compared with the first solubilization method, the non-ionic surfactant with polyoxyethylene groups shows a higher solubilization capacity.

[0091] The preparation method of the complexing composite includes: Mix 3% EDTA and 1.4% sodium hydroxide.

[0092] Comparative Example 2

[0093] The difference between this Comparative Example 2 and Example 1 lies in the preparation method of the rust inhibitor composite. The other conditions are the same. In this Comparative Example 2, the preparation method of the rust inhibitor composite includes mixing monocarboxylic acid and monoethanolamine in a volume ratio of 1:1, heating and stirring at 65 °C for 2 h to form a light yellow transparent liquid, and obtaining the rust inhibitor composite after cooling.

[0094] Table 1 Test Results of Examples

[0095]

[0096]

[0097]

[0098] According to the requirements of MT-76-2011, Examples 1 to 6 and Comparative Examples 1 to 3 were respectively configured into high-water-content hydraulic support hydraulic fluids with different hard waters at a mass fraction of 5%, and tested.

[0099] When the dilution hard water grade is 10, the test results are as follows:

[0100] Table 2: Test Results after Dilution with 10-Level Hard Water

[0101]

[0102]

[0103] Since rust stains appeared in Comparative Example 2 when the hardness grade was 10, it was not used subsequently. When the dilution hard water grade is 25, the test results are as follows:

[0104] Table 3: Test Results after Dilution with 25-Level Hard Water

[0105]

[0106]

[0107] To verify the antibacterial property of the present invention and extend the storage time, the results after placing at room temperature for 2 months are as follows:

[0108] Table 4. Results of Long-Term Placement

[0109]

[0110] It can be seen from the above results that the performance of the present invention meets the standard requirements, and at the same time has good water quality applicability, stability and environmental protection. No mold has been seen after placing at room temperature for 2 months. It can be seen that the antibacterial effect of the concentrated solution of the present invention is strong, which meets the requirements of current environmental protection and can promote the sustainable development of the coal industry.

[0111] The above content is only for explaining the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A concentrated liquid for a hydraulic support, characterized in that, It comprises the following components by mass percentage: Lubricating compound: 2% - 5% Rust preventive compound: 6% - 10% Complexing compound: 0.2% - 1.5% Defoamer: 0.02% - 0.1% Water: the balance; The lubricating compound includes fatty alcohol amide polyoxyethylene ether or polyoxyethylene ether carboxylic acid compounds.

2. The concentrated liquid for a hydraulic support according to claim 1, wherein The polyoxyethylene ether carboxylic acid compounds include one or a combination of two of castor oil polyoxyethylene ether carboxylic acid or fatty alcohol polyoxyethylene ether carboxylic acid.

3. The concentrated liquid for a hydraulic support according to claim 1, characterized in that, The rust preventive compound is prepared by mixing carboxylic acid and alkanolamine, followed by heating, stirring and cooling; the mass ratio of carboxylic acid to alkanolamine is 1:(1 - 2).

4. A concentrated liquid for a hydraulic support according to claim 3, characterized in that, The carboxylic acid includes a combination of two or more of monocarboxylic acid, dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.

5. A concentrated liquid for a hydraulic support according to claim 3, characterized in that The alkanolamine includes one or a combination of two of monoethanolamine, diethanolamine or triethanolamine.

6. The concentrated liquid for a hydraulic support according to claim 1, characterized in that, The complexing compound includes a combination of two or more of polyaspartic acid, tetrasodium glutamate diacetate or trisodium methylglycine diacetate.

7. A concentrated liquid for a hydraulic support according to claim 1, characterized in that, The defoamer includes a modified polysiloxane defoamer.

8. A method for preparing a concentrated liquid for a hydraulic support according to any one of claims 1 to 7, characterized in that, It includes adding water and complexing agent in proportion, stirring, then adding the lubricating compound and rust preventive compound and continuing to stir, and finally adding the defoamer and stirring to obtain the concentrated liquid for hydraulic supports.

9. The preparation method of a concentrated liquid for a hydraulic support according to claim 8, characterized in that, The stirring time is 40 - 120 min.

10. Application of the concentrated liquid according to any one of claims 1 to 7 in the field of transmission media for hydraulic supports.

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