A concentrated liquid for hydraulic support and a method for preparing the same

Abstract

The application provides a concentrated solution for hydraulic support, which is prepared from the following components by mass percentage: potassium ricinoleate soap, triethanolamine oleate soap, OP-10, triethanolamine, ethylene glycol, glycerol, benzotriazole, NaOH, sodium benzoate, sodium nitrite, hard water inhibitor, defoaming agent, and water. The hard water inhibitor is a mixture of methyl glycine diacetic acid and fulvic acid. The preparation method of the concentrated solution is as follows: the potassium ricinoleate soap and the triethanolamine oleate soap are stirred uniformly; then the OP-10 is added, and the triethanolamine is added and stirred uniformly; then the methyl glycine diacetic acid, the fulvic acid and the NaOH are added and stirred uniformly; then the ethylene glycol, the glycerol, the sodium nitrite, the benzotriazole, the sodium benzoate and water are added, and the mixture is heated to 70 DEG C under stirring until all the raw materials are dissolved, and then the mixture is cooled to 30 DEG C; finally, the defoaming agent is added, and the mixture is stirred uniformly until the solution is transparent.

Description

TECHNICAL FIELD

[0001] The present application relates to a concentrated liquid, in particular to a concentrated liquid for hydraulic support and a preparation method thereof. BACKGROUND

[0002] The hydraulic support is an important mechanical equipment for supporting the roof of the coal mining face in the coal industry, which is matched with the coal mining machine, not only realizes the comprehensive mechanization of coal mining, improves the efficiency of the coal mining and transportation equipment, but also maximally guarantees the life safety of the coal mine workers, the environment-friendly concentrated liquid for hydraulic support is the "blood" of the hydraulic support system, and the lifting, movement and cross protection of the hydraulic support need to apply the concentrated liquid for hydraulic support. The transmission medium of the concentrated liquid for hydraulic support is an important component of the hydraulic system, and the operation and efficiency of the hydraulic equipment cannot be separated from the concentrated liquid for hydraulic support, which directly affects the service life and safety of the equipment. If improper selection is made, the equipment will be damaged, and safety accidents will occur.

[0003] The coal industry standard MT76-2011 "emulsified oil, concentrated liquid and high water content hydraulic liquid for hydraulic support" stipulates the concentrated liquid product type suitable for the water quality according to the water hardness of different mines, but the water quality for liquid preparation is often unstable in actual production, and the change of the water quality for liquid preparation mainly includes the change of hardness and microbial colonies. At present, the existing technology mainly solves the problems of water hardness and colonies by adding an anti-hard water agent and a bactericide. However, the addition of excessive anti-hard water agent will cause the COD value of the concentrated liquid to increase, and in addition, the main type of the anti-hard water agent commonly added in the existing technology is EDTA, which is not easily biodegradable, which limits the green and clean development of the concentrated liquid for hydraulic support, and the addition of the bactericide will cause the skin irritation of the contact person, which brings inconvenience to production and use. SUMMARY

[0004] In order to solve the above technical problems, the present application provides a concentrated liquid for hydraulic support and a preparation method thereof. The concentrated liquid for hydraulic support of the present application has reasonable formula, simple preparation, green environmental protection, strong anti-hard water capacity, good antibacterial and anticorrosive effect, low COD value, complete biodegradability, non-toxic and non-pollution.

[0005] The purpose of the present application is to provide a concentrated liquid for hydraulic support, which is characterized in that the raw materials include the following components by mass percentage:

[0006]

[0007]

[0008] Preferably, the anti-hard water agent is a mixture of methyl glycine diacetic acid and fulvic acid, and the mass ratio of the two is methyl glycine diacetic acid: fulvic acid = 2-5: 1.

[0009] The concentrated solution for hydraulic support of the present application preferably has the following mass percentage of raw materials:

[0010]

[0011] The mass ratio of methyl glycine diacetic acid and fulvic acid in the anti-hard water agent is preferably 4:1.

[0012] The mass ratio of methyl glycine diacetic acid and fulvic acid in the anti-hard water agent is preferably 3:1.

[0013] The defoaming agent used in the concentrated solution of the present application can be any kind of conventional defoaming agent, and is preferably emulsified silicone oil.

[0014] The defoaming agent is preferably polyoxyethylene polyoxypropylene pentaerythritol ether.

[0015] The water used in the concentrated solution of the present application can be tap water or deionized water, and is preferably deionized water.

[0016] The preparation method of the concentrated solution for hydraulic support of the present application comprises the following steps:

[0017] (1) stirring the potassium castor oil soap and the triethanolamine oleate soap until they are uniformly mixed;

[0018] (2) adding OP-10 and stirring until it is uniformly mixed;

[0019] (3) adding triethanolamine and stirring until it is uniformly mixed;

[0020] (4) adding the anti-hard water agent and NaOH, and stirring at room temperature for 20-40 minutes until they are uniformly mixed;

[0021] (5) adding ethylene glycol, glycerol, sodium nitrite, benzotriazole and sodium benzoate, and stirring and heating to 60-80°C until all the raw materials are dissolved, and then cooling to 20-40°C;

[0022] (6) finally adding the defoaming agent, and stirring until the solution is clear.

[0023] The preparation method preferably comprises the following steps:

[0024] (1) stirring the potassium castor oil soap and the triethanolamine oleate soap until they are uniformly mixed;

[0025] (2) adding OP-10 and stirring until it is uniformly mixed;

[0026] (3) adding triethanolamine and stirring until it is uniformly mixed;

[0027] (4) adding methyl glycine diacetic acid, fulvic acid and NaOH, and stirring at room temperature for 30 minutes until they are uniformly mixed;

[0028] (5)Add ethylene glycol, glycerol, sodium nitrite, benzotriazole and sodium benzoate and water, stir and heat to 70℃ to dissolve the raw materials, then cool to 30℃;

[0029] (6)Finally add emulsified silicone oil, stir until the solution is clear.

[0030] The oleic acid triethanolamine soap in the present application can improve the lubricating property of the concentrated solution, but has poor stability. The present application found that the stability and lubricity of the castor oil acid potassium soap and the oleic acid triethanolamine soap are greatly improved. In addition, the present application selects OP-10, which is a polyethylene glycol type non-ionic surfactant. Compared with other types, OP-10 has better emulsifying property. OP-10 can reduce the oil soap precipitate in the concentrated solution during use, greatly enhancing the stability of the concentrated solution. Moreover, it is found through experiments that OP-10 has a synergistic effect when used in combination with the methyl glycine diacetate and fulvic acid in the present application, and can well resist high sulfate ion mine water. In the raw material compatibility, the present application uses ethylene glycol as a pour point depressant, which also has emulsifying property. Ethylene glycol has no irritating odor and can be mixed with water in any proportion, which improves the emulsifying property of the concentrated solution and reduces the freezing point of the product.

[0031] In practical application, the water content of the concentrated solution for hydraulic support can reach more than 95%. In addition, the hydraulic system is made of metal materials except for the non-metal pipeline and sealing elements. Moreover, it is difficult to maintain, maintain, repair and replace when used in the mine. Therefore, the concentrated solution has sufficient rust resistance, which is the key to ensure the normal use and prolong the service life of the hydraulic support. Therefore, in the formula of the concentrated solution, not only the adaptability of the rust resistance should be considered, but also the compatibility with other raw materials. The present application finally determines the following rust inhibitors through repeated experiments and screening: (1) sodium nitrite, which has strong oxidizing property and can cause anodic passivation of the metal, generating a dense oxide film on the surface to prevent rust. The aqueous solution of sodium nitrite is used as a corrosion inhibitor, and the rust prevention effect on cast iron is very obvious. (2) benzotriazole, which is a special corrosion inhibitor for copper and copper alloy. It forms a complex with monovalent copper. This complex is insoluble in water and organic solvents, so it can form an insoluble transparent cover film on the surface of copper and copper alloy. This complex film prevents the dissolution of copper. The chemical adsorption film formed on the metal surface has a desorption energy 17 times greater than the adsorption energy, so the adsorption is easy and the desorption is difficult, and the inertness is very large, so it can effectively protect the copper metal for a long time. (3) triethanolamine, which is an emulsifier and a rust inhibitor, can be used to prepare a corrosion inhibitor to protect the metal surface and prevent oxidation. (4) sodium benzoate, which can prevent rust and corrosion.

[0032] Because EDTA is not easy to be biodegraded, the present application finds through a large number of tests that the combination of methyl glycine diacetic acid and fulvic acid is used to resist high sulfate ion and high hardness mine water, which not only reduces the dosage compared with EDTA, but also can simultaneously play the roles of antibiosis and COD reduction. The methyl glycine diacetic acid used in the present application is referred to as MGDA. It is a small molecule chelating agent, is easy to be biodegraded, and is non-toxic. The fulvic acid is a group of relatively small molecular weight humic substances, can be dissolved in dilute alkali solution, can be dissolved in acid and water, has aromatic, aliphatic and various functional group structural characteristics. According to different sources, the fulvic acid is mainly divided into two kinds of mineral source fulvic acid and biological source fulvic acid. The fulvic acid has multiple functional groups, complex composition, and diverse structure, and the good biochemical characteristics make it play a great role in industry, agriculture, medical and health industry and animal husbandry. However, so far no one has tried to use the fulvic acid for the concentrated liquid for hydraulic support. The present application combines the methyl glycine diacetic acid and the fulvic acid, and the two play a synergistic effect. Only about one third of the amount of EDTA is used, and a good effect of resisting hard water is achieved. In addition, the antibiosis and COD reduction effects are also achieved, and a good antibacterial effect can be achieved without adding a bacteriostatic agent. At the same time, the lubricating property of the concentrated liquid is also improved.

[0033] Generally, the user uses the concentrated liquid in the mine site by using the mine water of the mine, or the mine water is treated first and then used to prepare the liquid.

[0034] Beneficial effects

[0035] The concentrated liquid of the present application has very good stability, lubricity, rust prevention and corrosion resistance, effectively inhibits the precipitation of oil and soap in the site liquid preparation and use, and by using the hard water resistant agent of the present application, in the case that the amount is one third of the conventional hard water resistant agent, high sulfate ion and high hardness mine water can be well resisted, and COD reduction and bacteriostasis are simultaneously achieved, and the lubricity is also improved. The concentrated liquid formula of the present application is reasonable, the components complement each other, and the raw materials are green and environmentally friendly and conducive to biodegradation. The use of complexing agents and surfactants can resist high sulfate ion and high hardness mine water. The combination of organic salt rust inhibitor and inorganic salt rust inhibitor can overcome the corrosion of cast iron and achieve good rust prevention effect; the addition of special copper corrosion inhibitor can effectively protect copper metal. The addition of pour point depressant not only improves the emulsifying property of the product, but also greatly reduces the freezing point of the product, which is suitable for use in areas with lower temperature. DETAILED DESCRIPTION

[0036] The technical scheme of the present application and its effects are further described through specific examples. The following examples are used to illustrate the content of the present application, and are not used to limit the protection scope of the present application. Simple changes made by applying the concept of the present application are within the scope of protection of the present application.

[0037] The equipment used in the preparation method of the present application can be the commonly known equipment in the art. The raw materials used in the present application are commercially available unless otherwise specified.

[0038] Example 1

[0039] The concentrated liquid for hydraulic support of the present example is characterized in that the mass percentage of the raw materials is as follows:

[0040]

[0041]

[0042] The anti-hard water agent is a combination of methyl glycine diacetic acid and fulvic acid in a mass ratio of 4:1.

[0043] The preparation method of the concentrated liquid for hydraulic support of the present example comprises the following steps:

[0044] (1) stirring the potassium castor oil soap and the triethanolamine oleate soap uniformly;

[0045] (2) adding OP-10 and stirring uniformly;

[0046] (3) adding triethanolamine and stirring uniformly;

[0047] (4) adding methyl glycine diacetic acid, fulvic acid and NaOH, and stirring at room temperature for 30 min until uniform;

[0048] (5) adding ethylene glycol, glycerol, sodium nitrite, benzotriazole and sodium benzoate and deionized water, stirring and heating to 70°C to dissolve the raw materials, and then cooling to 30°C;

[0049] (6) finally adding emulsified silicone oil, stirring until the solution is clear.

[0050] Example 2

[0051] The concentrated liquid for hydraulic support of the present example is characterized in that the mass percentage of the raw materials is as follows:

[0052]

[0053]

[0054] The balance is deionized water.

[0055] The anti-hard water agent is a combination of methyl glycine diacetic acid and fulvic acid in a mass ratio of 4:1.

[0056] The preparation method of the concentrated liquid for hydraulic support of the present example comprises the following steps:

[0057] (1) Stir the potassium castor oil acid soap and triethanolamine oleate soap evenly;

[0058] (2) Add OP-10 again and stir evenly;

[0059] (3) Add triethanolamine again and stir evenly;

[0060] (4) Add methyl glycine diacetic acid, fulvic acid, and NaOH again, and stir at room temperature for 30 min until evenly stirred;

[0061] (5) Add ethylene glycol, glycerol, sodium nitrite, benzotriazole, and sodium benzoate and deionized water again, stir and heat to 80°C to dissolve the various raw materials, and then cool to 40°C;

[0062] (6) Finally, add polyoxyethylene polyoxypropylene pentaerythritol ether, stir until the solution is clear, and obtain.

[0063] Example 3

[0064] The concentrated liquid for hydraulic supports of the present example is characterized in that the mass percentage of the raw materials is:

[0065]

[0066]

[0067] The anti-hard water agent is a combination of methyl glycine diacetic acid and fulvic acid in a mass ratio of 3:1.

[0068] The preparation method of the concentrated liquid for hydraulic supports of the present example includes the following steps:

[0069] (1) Stir the potassium castor oil acid soap and triethanolamine oleate soap evenly;

[0070] (2) Add OP-10 again and stir evenly;

[0071] (3) Add triethanolamine again and stir evenly;

[0072] (4) Add methyl glycine diacetic acid, fulvic acid, and NaOH again, and stir at room temperature for 30 min until evenly stirred;

[0073] (5) Add ethylene glycol, glycerol, sodium nitrite, benzotriazole, and sodium benzoate and deionized water again, stir and heat to 75°C to dissolve the various raw materials, and then cool to 35°C;

[0074] (6) Finally, add emulsified silicone oil, stir until the solution is clear, and obtain.

[0075] Comparative Example 1

[0076] The anti-hard water agent in Example 1 (i.e. a mixture of methyl glycine diacetic acid and fulvic acid) is replaced by a single EDTA, and other contents include the mass percentage of the hard water agent in the formula (3%), as well as other raw materials and respective proportions, and the preparation method is the same as that of Example 1.

[0077] Comparative Example 2

[0078] The amount of EDTA in the formula of Comparative Example 1 is changed to 8% of the total mass of raw materials, and other contents are the same as those of Comparative Example 1.

[0079] According to the requirements of the coal industry standard MT76-2011 "Emulsified oil, concentrated liquid and high water content hydraulic liquid for hydraulic support", the concentrated liquid prepared in Example 1 is tested for related performance. The sulfate content of the artificial hard water prepared in this experiment is 2000 mg / L.

[0080] Table 1

[0081]

[0082] The concentrated liquids of Examples 2-3 and Comparative Examples 1-2 are also tested for related performance according to the same method as Example 1 according to MT76-2011, and the results are shown in the following table:

[0083] Table 2

[0084]

[0085]

[0086] As can be seen from Table 2, when the anti-hard water agent of the present application is replaced by the same amount of EDTA, the anti-hard water effect is obviously decreased, and white precipitates appear in the stability experiment, and the water is turbid. When the amount of EDTA is increased to 8%, no precipitates are obtained. In addition, the lubricity of the concentrated liquid using the anti-hard water agent of the present application is also improved compared with using EDTA.

[0087] The concentrated liquids of Examples 1-3 and Comparative Examples 1-2 above are respectively mixed with the artificial hard water prepared in the above experiment according to the ratio of 5% concentrated liquid and 95% artificial hard water to form high water content hydraulic liquid. Then, the COD of each high water content hydraulic liquid is tested. The test standard is HJ 828-2017 "Determination of chemical oxygen demand in water by potassium dichromate method", and the test results are shown in the following table:

[0088] Table 3

[0089] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 COD value (mg / L) 5100 5500 5400 9800 11000

[0090] As shown in Table 3, the COD values of Examples 1-3 are obviously lower than those of Comparative Examples 1-3, which indicates that the hard water resistance agent of the present application can significantly reduce the COD value of the concentrated solution.

[0091] Examples 1-3 and Comparative Examples 1 and 2 were also tested for their bacteriostatic performance. Specifically, samples 1-3 and Comparative Examples 1 and 2 were each prepared into 5% high water content hydraulic fluid using water from the same mine (the water from the mine has a hardness of 500 mg / L, and the total bacterial count of the water is about 350 CFU / ml), and were placed in a volumetric flask and shaken in a constant temperature shaker (36±1℃). After 28 days, the total bacterial count was recorded. Each test sample was provided in triplicate, and the average value was finally calculated. The statistical results are shown in Table 4.

[0092] Table 4

[0093] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Total number of colonies 35 28 52 >3000 >4000

[0094] As shown in Table 4, after 28 days, the total bacterial count of Examples 1-3 has obviously decreased, which indicates that they have good bacteriostatic performance. However, the total bacterial count of Comparative Examples 1 and 2 has increased by about ten times. The total bacterial count of Comparative Example 2 is even higher than that of Comparative Example 1. The above data proves that the hard water resistance agent added in the present application also has good bacteriostatic performance.

[0095] It should be noted that the above only lists several specific embodiments of the present application, and obviously the present application is not limited to the above embodiments, but can also have other variations. All variations directly derived or indirectly inferred from the disclosure of the present application by those skilled in the art should be considered as falling within the protection scope of the present application.

Claims

1. A concentrated fluid for hydraulic supports, characterized in that... Its raw materials, by mass percentage, include the following components: The remainder is water; The water hardness agent is a mixture of methylglycine diacetic acid and fulvic acid, wherein the mass ratio of the two is methylglycine diacetic acid: fulvic acid = 2-5:

1.

2. The concentrated fluid for hydraulic supports as described in claim 1, characterized in that... The mass percentage of the raw materials mentioned is: The remainder is water.

3. The concentrated fluid for hydraulic supports as described in claim 2, characterized in that... The mass ratio of methylglycine diacetic acid and fulvic acid in the described anti-hard water agent is 4:

1.

4. The concentrated fluid for hydraulic supports as described in claim 2, characterized in that... The mass ratio of methylglycine diacetic acid to fulvic acid in the described anti-hard water agent is 3:

1.

5. The concentrated fluid for hydraulic supports as described in claim 1, characterized in that... The defoamer mentioned is emulsified silicone oil.

6. The concentrated fluid for hydraulic supports as described in claim 1, characterized in that... The defoamer mentioned is polyoxyethylene polyoxypropylene pentaerythritol ether.

7. The concentrated fluid for hydraulic supports as described in claim 1, characterized in that... The water described is deionized water.

8. The method for preparing the concentrated fluid for hydraulic supports as described in any one of claims 1 to 7, characterized in that: Includes the following steps: (1) Stir the potassium castor oil soap and triethanolamine oleate soap evenly; (2) Add OP-10 and stir well; (3) Add triethanolamine and stir well; (4) Add the anti-hardening agent and NaOH, and stir at room temperature for 20-40 minutes until the mixture is uniform; (5) Add ethylene glycol, glycerol, sodium nitrite, benzotriazole, sodium benzoate and water, stir and heat to 60-80℃ to dissolve the various raw materials, and then cool to 20-40℃; (6) Finally, add the defoamer and stir until the solution is clear.

9. The method for preparing the concentrated fluid for hydraulic supports as described in claim 8, characterized in that: Includes the following steps: (1) Stir the potassium castor oil soap and triethanolamine oleate soap evenly; (2) Add OP-10 and stir well; (3) Add triethanolamine and stir well; (4) Add methylglycine diacetic acid, fulvic acid, and NaOH, and stir at room temperature for 30 minutes until the mixture is homogeneous. (5) Add ethylene glycol, glycerol, sodium nitrite, benzotriazole, sodium benzoate and water, stir and heat to 70°C to dissolve the various raw materials, and then cool to 30°C; (6) Finally, add emulsified silicone oil and stir until the solution is clear.

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