CN114686293B - High-hardness water-resistant hydraulic support concentrated solution and preparation method thereof - Google Patents

High-hardness water-resistant hydraulic support concentrated solution and preparation method thereof Download PDF

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CN114686293B
CN114686293B CN202210273089.3A CN202210273089A CN114686293B CN 114686293 B CN114686293 B CN 114686293B CN 202210273089 A CN202210273089 A CN 202210273089A CN 114686293 B CN114686293 B CN 114686293B
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hydraulic support
hard water
water
polyethylene glycol
concentrated solution
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CN114686293A (en
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刘鲤粽
沈栋
白飞飞
于维雨
孙刚
任越
黄澎
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CCTEG China Coal Research Institute
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CCTEG China Coal Research Institute
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/18—Anti-foaming property
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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Abstract

The invention relates to a high hard water resistant hydraulic support concentrated solution and a preparation method thereof, wherein the hydraulic support concentrated solution comprises the following raw materials in percentage by weight: hydroxy cellulose: 2 to 10 percent; long-chain dibasic acid polyethylene glycol ester: 2 to 10 percent; water-soluble polyvinyl alcohol: 2 to 5 percent; monoethanolamine: 2 to 5 percent; aqueous polyurethane: 2 to 5 percent; boric acid: 2 to 5 percent; octanoic acid: 1 to 5 percent; ethylene glycol: 1 to 5 percent; benzotriazole: 0.05% -0.1%; hydrophilic modified nano carbon microspheres: 0.01 to 0.03 percent; tap water: and (4) the balance. The raw materials adopted by the invention are all nonionic compounds, have extremely high hard water resistance and can resist hard water with the hardness level of 30 of artificial hard water.

Description

High-hardness water resistant hydraulic support concentrated solution and preparation method thereof
Technical Field
The invention belongs to the field of hydraulic fluid for lubricating transmission media, and particularly relates to a green environment-friendly nonionic high-hardness water-resistant hydraulic support concentrated solution and a preparation method thereof.
Background
The hydraulic support is a structure used for controlling the mine pressure of a coal face, hydraulic support liquid is a working medium of the hydraulic support, the lubricating property and the emulsifying property of the hydraulic support liquid are increased by adopting an anionic surfactant mostly, and as mine water is required to be added in a formula of a hydraulic support concentrated solution as a carrier, the hardness of a lot of mine water is relatively high, and some mine water has the hardness even reaching more than 1500mg/L (artificial hardness 30). The anionic surfactant of the common hydraulic support liquid is easy to form insoluble soap with calcium and magnesium ions in mine water, so that the insoluble soap precipitates out of working liquid, a filter and a valve core are blocked, the lubricating and antirust performance of a diluent is reduced, the use of hydraulic equipment is influenced, and even the whole hydraulic support system is paralyzed.
In order to solve the problem of the soaping out, a nonionic surfactant is added into a hydraulic support concentrated solution in the related art, but the nonionic surfactant is bonded with a substrate by virtue of Van der Waals force, so that the bonding strength of an adsorption film is weaker, and the bearing capacity of the nonionic surfactant is poorer due to the problems.
Based on the above-mentioned related technologies, there is a need to develop a high-hardness water (capable of withstanding artificial hardness of 30), good stability, and good load-bearing performance (P) B ) A preferred hydraulic stent concentrate.
Disclosure of Invention
The invention aims to provide a green environment-friendly water-based hydraulic support solution in a high-hardness water environment and a preparation method thereof. The invention meets the standard of emulsified oil, concentrated solution and high-water-content hydraulic fluid for MT 76-2011 hydraulic supports, has stable property, easy biodegradation and environmental protection, and the preparation method of the hydraulic fluid is simple and meets the requirement of industrial large-scale production.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
the embodiment of the invention provides a high hard water resistant hydraulic support concentrated solution, which comprises the following raw materials in percentage by weight:
Figure BDA0003554603540000011
Figure BDA0003554603540000021
the invention reasonably constructs the formula of the hydraulic support concentrated solution. Thereby solving the problem of soaping-out and improving the bearing performance (P) B ) Two core problems. First, the present invention uses a nonionic surfactant, which does not dissociate into anions or cations having a band point in an aqueous solutionBut rather exist in a neutral nonionic molecular or micellar state. The problem of the soaping-out is fundamentally solved. Secondly, the hydrophilic modified nano carbon microspheres are added to generate a synergistic effect with the waterborne polyurethane, so that the extreme pressure performance of the hydraulic fluid is improved. The nano carbon microsphere has the porous performance, so that the slow release capability of benzotriazole can be improved, and the corrosion resistance of the hydraulic fluid is further improved. The nano carbon microspheres have porous characteristics and can adsorb metal ions such as calcium, magnesium and the like, and the use of the hydraulic fluid in a harsh high-hardness water environment is widened. The problems that the load-bearing capacity is poor and the corrosion resistance and the rust resistance of the hydraulic concentrated solution are poor (the surface of a metal substrate is exposed in the environment of corrosion factors such as air, water and the like due to the cleaning effect of the nonionic surfactant) because the nonionic surfactant (the nonionic surfactant is combined with the substrate by virtue of Van der Waals force, and the bonding strength is weak and the strength of an adsorption film is low) is adopted are effectively solved.
Through reasonable construction of the formula, the emulsified oil, the concentrated solution and the high-water-content hydraulic liquid for the MT 76-2011 hydraulic support can still meet the standard of emulsified oil, concentrated solution and high-water-content hydraulic liquid for the MT 76-2011 hydraulic support under a high-hardness water system with the water hardness of 1500mg/L (artificial hardness classification of 30), and the emulsified oil, the concentrated solution and the high-water-content hydraulic liquid for the MT 76-2011 hydraulic support are stable in property, have good biodegradability and are environment-friendly.
In some embodiments of the present invention, the hydrophilic modified nanocarbon microsphere is formed by introducing hydrophilic polar groups into a bulk structural group of the nanocarbon microsphere, wherein the hydrophilic polar groups include nitro groups, hydroxyl groups, amino groups, amide groups, and the like.
In some embodiments of the present invention, the hydrophilic modified nano carbon microsphere has a particle size of 400 to 500nm and a specific surface area of 1000 to 1200m 2 The pore volume is 0.85-0.9mL/g, and the most probable pore diameter is 1.6-2.0nm.
The nano carbon microspheres of the invention generate a synergistic effect with waterborne polyurethane, and improve the extreme pressure performance of hydraulic fluid. The nano carbon microsphere has the porous performance, so that the slow release capability of benzotriazole can be improved, and the corrosion resistance of the hydraulic fluid is further improved. The nano carbon microsphere has porous characteristic and can adsorb metal ions such as calcium, magnesium and the like, so that the use of the hydraulic fluid in harsh high-hardness water environment is widened.
In some embodiments of the present invention, the hydrophilic modified nano carbon microspheres are prepared by using carbon microspheres with a particle size range of 500-10000nm (such as 500-1000nm, 500-2000nm, 1000-10000nm, etc.) as a raw material (such as KBN-CA-002 type carbon microspheres from cabernet (suzhou) composite limited), ultrasonically mixing the raw material with ethanol for 1h, and drying in a vacuum drying oven at 60 ℃ for 12h after suction filtration for later use. 1g of the washed carbon microspheres and 40ml of 65 percent concentrated HNO are taken 3 And 120ml of concentrated 98% 2 SO 4 And (3) carrying out ultrasonic oscillation mixing reaction for 1h at 80 ℃, washing the carbon microsphere deionized water to be neutral after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for 12h for later use. Putting 0.8g of hydroxyl-acidified carbon microspheres, 5g of glucose, 1g of acrylamide and 50ml of distilled water into a reaction kettle, heating at 180 ℃ for 12h, cooling, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃ for 12h for later use. 0.5g of modified carbon microsphere is taken and soaked in 30ml of ammonium persulfate solution at room temperature for 3h, after the reaction is finished, the carbon microsphere is cleaned by deionized water and dried in a vacuum drying oven at 60 ℃ for 12h, and then the hydrophilic nano carbon microsphere is prepared.
In some embodiments of the present invention, the hydroxy cellulose is one or a combination of two or more of hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose. Hydroxycellulose has good lubricity while also having excellent degradability.
In some embodiments of the present invention, the long-chain dibasic acid polyethylene glycol ester refers to a dibasic acid polyethylene glycol ester containing more than 10 carbon atoms. In some embodiments of the present invention, the long-chain dibasic acid polyethylene glycol ester is one or a combination of two or more of sebacic acid polyethylene glycol 600 monoester, dodecanedioic acid polyethylene glycol 600 monoester, tridecanedioic acid polyethylene glycol 600 monoester, and dimer acid polyethylene glycol 600 monoester. The long-chain dibasic acid polyethylene glycol ester has good lubricity and excellent degradability.
In some embodiments of the invention, the aqueous polyurethane is a two-component aqueous polyurethane containing-NCO groups and-OH groups in the molecular structure. In some embodiments of the invention, the aqueous polyurethane is PU-600R, PU-300B, HC-38, shanghai Yangtze chemical engineering science and technology Limited.
The waterborne polyurethane used in the invention takes water as a solvent, has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, has excellent film forming property on the surface of metal, and has an important effect on improving the antirust capacity of hydraulic fluid. The invention discovers that when aqueous polyurethane is used as one of the formulations in the hydraulic bracket concentrated solution, the lubricity of the system can be improved while the anti-corrosion capability is increased, and the maximum non-seizing P is increased B The value is obtained.
In the above concentrated solution for hydraulic bracket, preferably, the weight percentage of the raw materials is:
Figure BDA0003554603540000031
Figure BDA0003554603540000041
the embodiment of the invention also provides a preparation method of the hydraulic support concentrated solution, which comprises the following steps:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10-30min at room temperature until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxy cellulose, long-chain dibasic acid polyethylene glycol ester and ethylene glycol, heating to 60-80 ℃, adding the rest water, and stirring for 10-30min until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, stirring for 10-30min, and cooling to obtain the hydraulic support concentrated solution.
The embodiment of the invention also provides application of the hydraulic support concentrated solution in a high-hardness water environment, wherein the hardness of hard water is 750-1500mg/L.
In the invention, all raw materials are nonionic surfactants, wherein the hydroxy cellulose and the long-chain dibasic acid polyethylene glycol ester mainly play a lubricating role; the waterborne polyurethane has the functions of film forming, film strength improvement and rust prevention; the water-soluble polyvinyl alcohol and the ethylene glycol mainly play roles in auxiliary film formation and auxiliary lubrication; monoethanolamine is used as a conventional reagent to play roles in adjusting the pH value and solubilizing; boric acid mainly plays a role in corrosion prevention; the octanoic acid mainly has the functions of rust prevention and defoaming; benzotriazole mainly plays a role in corrosion prevention.
The invention has the advantages and beneficial effects that:
1) The hydroxyl cellulose and the like adopted as raw materials have hydrophilicity, and can form a uniform, transparent and stable system in an aqueous solution.
2) The raw materials adopted by the invention are all nonionic compounds, have extremely high hard water resistance, and can resist hard water with the hardness level of 30 (the water hardness is 1500 mg/L) of artificial hard water.
3) The lubricating oil has good lubricity, the maximum non-seizure load (PB) of the hydraulic support liquid is measured by measuring the bearing capacity of a GB/T3142-2019 lubricating agent, and the PB value of the lubricating oil can reach 392N under the condition that concentrated liquid is diluted by hard water by 20 times (5% of stock solution concentration).
4) The invention has good biodegradability, and the hydroxycellulose, the long-chain dibasic acid polyethylene glycol ester and the polyvinyl alcohol are easy to dissolve in water and are biodegradable.
Drawings
Fig. 1 is SEM image of hydrophilic modified nano carbon microsphere.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The embodiment of the invention provides a high hard water resistant hydraulic support concentrated solution, which comprises the following raw materials in percentage by weight:
Figure BDA0003554603540000051
through reasonable construction of the formula, the emulsified oil, the concentrated solution and the high-water-content hydraulic liquid for the MT 76-2011 hydraulic support can still meet the standard of emulsified oil, concentrated solution and high-water-content hydraulic liquid for the MT 76-2011 hydraulic support under a high-hardness water system with the water hardness of 1500mg/L (artificial hardness classification of 30), and the emulsified oil, the concentrated solution and the high-water-content hydraulic liquid for the MT 76-2011 hydraulic support are stable in property, have good biodegradability and are environment-friendly.
In some embodiments of the present invention, the hydrophilic modified nano carbon microsphere is an amphiphilic carbon microsphere with a nitrate group, a hydroxyl group, an amino group and an amide group polar group introduced into a bulk structural group of the nano carbon microsphere, and a water-soluble content of the amphiphilic carbon microsphere is greater than or equal to 70%. In some embodiments of the present invention, the hydrophilic modified nano carbon microsphere has a particle size of 400 to 500nm and a specific surface area of 1000 to 1200m 2 The pore volume is 0.85-0.9mL/g, and the most probable pore diameter is 1.6-2.0nm. The nano carbon microspheres and the waterborne polyurethane generate a synergistic effect, and the extreme pressure performance of the hydraulic fluid is improved. The nano carbon microspheres have porous performance, so that the slow release capacity of benzotriazole can be improved, and the corrosion resistance of the hydraulic fluid is further improved. The nano carbon microspheres have porous characteristics and can adsorb metal ions such as calcium, magnesium and the like, and the use of the hydraulic fluid in a harsh high-hardness water environment is widened.
In some embodiments, the hydroxy cellulose is one or a combination of two or more of hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose. Hydroxycellulose has good lubricity while also having excellent degradability.
In some embodiments, the long-chain diacid polyglycol ester refers to a diacid polyglycol ester containing more than 10 carbon atoms. In some embodiments of the present invention, the long-chain dibasic acid polyethylene glycol ester is one or a combination of two or more of sebacic acid polyethylene glycol 600 monoester, dodecanedioic acid polyethylene glycol 600 monoester, tridecanedioic acid polyethylene glycol 600 monoester, and dimer acid polyethylene glycol 600 monoester. The long-chain dibasic acid polyethylene glycol ester has good lubricity and excellent degradability.
In some embodiments, the aqueous polyurethane is a two-component aqueous polyurethane containing-NCO groups and-OH groups in the molecular structure. In some embodiments of the invention, the aqueous polyurethane is PU-600R, PU-300B, HC-38, etc., which is a new material science and technology company, heifeng, yongchang chemical science and technology company, inc.
The waterborne polyurethane used in the invention takes water as a solvent, has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like, has excellent film forming property on the surface of metal, and has an important effect on improving the antirust capacity of hydraulic fluid. The invention discovers that when aqueous polyurethane is used as one of the formulations in the hydraulic bracket concentrated solution, the lubricity of the system can be improved while the anti-corrosion capability is increased, and the maximum non-seizing P is increased B The value is obtained.
The embodiment of the invention also provides a preparation method of the hydraulic support concentrated solution, which comprises the following steps:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10-30min at room temperature until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxy cellulose, long-chain dibasic acid polyethylene glycol ester and ethylene glycol, heating to 60-80 ℃, adding the rest water, and stirring for 10-30min until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, stirring for 10-30min, and cooling to obtain the hydraulic support concentrated solution.
The embodiment of the invention also provides application of the hydraulic support concentrated solution in a high-hardness water environment, wherein the hardness of hard water is 750-1500mg/L.
The preparation method of the hydrophilic modified nano carbon microspheres adopted in the embodiments 1 to 3 of the invention comprises the following steps:
using carbon microsphere whose grain size range is 500-2000nm as raw materialUltrasonically mixing the carbon microsphere raw material with ethanol for 1h, filtering, and drying in a vacuum drying oven at 60 ℃ for 12h for later use. 1g of washed carbon microspheres and 40ml of 65% concentrated HNO 3 And 120ml of concentrated 98% 2 SO 4 And (3) carrying out ultrasonic oscillation mixing reaction for 1h at 80 ℃, washing the carbon microsphere deionized water to be neutral after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for 12h for later use. Putting 0.8g of hydroxyl-acidified carbon microspheres, 5g of glucose, 1g of acrylamide and 50ml of distilled water into a reaction kettle, heating at 180 ℃ for 12h, cooling, washing with deionized water and ethanol, and drying in a vacuum drying oven at 60 ℃ for 12h for later use. 0.5g of modified carbon microsphere is taken and soaked in 30ml of ammonium persulfate solution at room temperature for 3h, after the reaction is finished, the carbon microsphere is cleaned by deionized water and dried in a vacuum drying oven at the temperature of 60 ℃ for 12h to obtain the hydrophilic modified nano carbon microsphere, wherein the particle size range is 400-500nm.
The SEM image of the hydrophilic modified nano carbon microsphere is shown in the figure 1, and the properties of the hydrophilic modified nano carbon microsphere are shown in the table 1.
TABLE 1 Hydrophilically modified nanocarbon microsphere Properties
Particle size/nm Specific surface area/m 2 /g Pore volume/mL/g Most probable pore diameter/nm
400-500 1000-1200 0.85-0.9 1.6-2.0
The present invention will be further illustrated with reference to the following examples.
The formulations of the examples and the comparative examples are evaluated according to the standard of MT/T76-2011 emulsified oil, concentrated solution and high-water-content hydraulic fluid for hydraulic supports. The method is characterized in that the maximum non-seizure load (PB) of the hydraulic support solution is measured by measuring the bearing capacity of a GB/T3142-2019 lubricant, wherein detection items 1-7 are detection items aiming at a stock solution of the hydraulic support concentrate, and detection items 8-16 are detection items aiming at a high-water-content hydraulic solution obtained by diluting the hydraulic support concentrate by 20 times of hard water (the hardness grade of artificial hard water is 30, and the hardness of water is 1500 mg/L).
Example 1
Preparing a hydraulic support concentrated solution, wherein the hydraulic support concentrated solution comprises the following raw materials in percentage by mass:
Figure BDA0003554603540000071
the preparation method of the hydraulic support concentrated solution comprises the following steps:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxyethyl cellulose, dimer acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, and stirring for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The product performance of the formula is evaluated according to the standard of MT/T76-2011 emulsified oil, concentrated solution and high-water-content hydraulic fluid for hydraulic supports. The results are shown in Table 2. All properties are excellent, the standard requirements are met, and the hard water resistance is excellent.
Table 2 evaluation results of example 1
Figure BDA0003554603540000072
Figure BDA0003554603540000081
Example 2
Preparing a hydraulic support concentrated solution, wherein the hydraulic support concentrated solution comprises the following raw materials in percentage by mass:
Figure BDA0003554603540000082
Figure BDA0003554603540000091
the preparation steps are as follows:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxypropyl methylcellulose, dodecanedioic acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, and stirring for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The formulations were evaluated for product performance as MT/T76. The results are shown in Table 3. The product has excellent performance, meets the standard requirements, and has excellent hard water resistance.
Table 3 example 2 evaluation results
Figure BDA0003554603540000092
Figure BDA0003554603540000101
Example 3
Preparing a hydraulic support concentrated solution, wherein the hydraulic support concentrated solution comprises the following raw materials in percentage by mass:
Figure BDA0003554603540000102
the preparation steps are as follows:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxypropyl methylcellulose, dimer acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, and stirring for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The product performance of the formulation was evaluated as MT/T76. The results are shown in Table 4. The product has excellent performance, meets the standard requirements, and has excellent hard water resistance.
Table 4 example 3 evaluation results
Figure BDA0003554603540000111
Figure BDA0003554603540000121
Comparative example 1 (no hydrophilic modified nanocarbon microspheres added compared to example 1):
preparing a concentrated solution, wherein the weight of each raw material is as follows:
Figure BDA0003554603540000122
the preparation steps are as follows:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxyethyl cellulose, dimer acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) And adding benzotriazole, stirring for 30 minutes, and cooling to obtain the non-ionic hydraulic bracket concentrated solution.
The comparative formulation was evaluated for product performance as MT/T76. The results are shown in Table 5. Although the system meets the MT/T76 index requirement, the extreme pressure performance is reduced, and P B The value drops from 430 to 392.
Table 5 evaluation results of comparative example 1
Figure BDA0003554603540000123
Figure BDA0003554603540000131
Comparative example 2 (no hydrophilic modified nanocarbon microspheres added compared to example 2):
preparing a concentrated solution, wherein the weight of each raw material is as follows:
Figure BDA0003554603540000132
Figure BDA0003554603540000141
the preparation steps are as follows:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxypropyl methylcellulose, dodecanedioic acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Benzotriazole was added and stirred for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The product performance of the formulation was evaluated as MT/T76. The results are shown in Table 6. Decrease in lubricating properties, P B The values do not meet the MT/T76 standard requirements.
Table 6 evaluation results of comparative example 2
Figure BDA0003554603540000142
Figure BDA0003554603540000151
Comparative example 3 (compared to example 1, no hydrophilic modified nanocarbon microspheres, aqueous polyurethane added):
preparing a concentrated solution, wherein the weight of each raw material is as follows:
Figure BDA0003554603540000152
the preparation steps are as follows:
(1) Adding 30% of water and monoethanolamine according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxyethyl cellulose, dimer acid polyethylene glycol 600 monoester and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Benzotriazole was added and stirred for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The comparative formulation was evaluated for product performance as MT/T76. The results are shown in Table 7. The corrosion resistance and the lubricity of the system do not meet the requirements of MT/T76.
Table 7 evaluation results of comparative example 3
Figure BDA0003554603540000161
Comparative example 4
Preparing a concentrated solution, wherein the weight of each raw material is as follows:
Figure BDA0003554603540000162
Figure BDA0003554603540000171
the preparation steps are as follows:
(1) Adding 30% of water, monoethanolamine and triethanolamine oleate soap according to the proportion, and stirring for 10min until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol and ethylene glycol, heating to 60 ℃, adding the rest water, and stirring for 30 minutes until the mixture is clear;
(3) Benzotriazole was added and stirred for 30 minutes. And cooling to obtain the non-ionic hydraulic support concentrated solution.
The comparative formulation was evaluated for product performance at MT/T76. The results are shown in Table 8. The system has the hardness grade of 30 resistant to artificial hard water, the hard water capacity of 1500mg/L water hardness is poor, and the stability and the dispersibility can not meet the requirements of MT/T76.
Table 8 evaluation results of comparative example 4
Figure BDA0003554603540000172
Figure BDA0003554603540000181
Biodegradation test
The biodegradation evaluation is carried out by adopting reference GB/T20778-2006, and CO is not contained in a bottle filled with activated sludge and a test substance 2 In a constant-temperature water bath at the temperature of (25 +/-1) DEG C, the oxygen-consuming microorganisms take carbon in a test object as a nutrient substance, and under the oxidation action of enzymes in vivo, the long chain is changed into the short chain, and finally the long chain is decomposed into CO 2 And water. Evaluation by biodegradation Rate AS and biodegradability index IBThe degradability of the hydraulic fluid was also referenced to the assay standard used for the complete biodegradation test, as shown in table 9. The higher the biodegradation rate, the less toxic to the environment. The experiment adopts sludge to provide activated sludge for water control, the supernatant is removed after 3 days of aeration, 100ml of uniform sludge is taken before the experiment, the sludge is filtered after precipitation, and filter residue is dried and weighed for use. The measurements were carried out according to the standard GB/T20778-2006, the results of which are shown in Table 10. The results show that the formulation of example 1 and the formulation of example 2 both have excellent biodegradability, and also show that the hydraulic stent concentrate based on the formulation system has good biodegradability.
TABLE 9 biodegradable Property measurement standards
Degradation property Is difficult to be biodegraded Is biodegradable Is easy to be biologically degraded
Index of degradation rate η 10d ＞10％ η 10d ＞10％,η 28d ＜60％ η 10d ＞10％,η 28d ＞60％
TABLE 10 evaluation results of biodegradation Properties
Assay substance Percent degradation rate% Degradability Evaluation results
Example 1 formulation 73.47 188.4 Is easy to be biologically degraded
Example 2 formulation 69.65 178.6 Is easy to be biologically degraded
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The utility model provides a high hard water resistant hydraulic support concentrate which characterized in that: the hydraulic support concentrated solution comprises the following raw materials in percentage by weight:
Figure FDA0003554603530000011
2. the high hard water resistant hydraulic support concentrate of claim 1, wherein: the hydrophilic modified nano carbon microsphere is formed by introducing hydrophilic polar groups into a carbon microsphere body structural group, wherein the hydrophilic polar groups comprise nitryl, hydroxyl, amino and acylamino.
3. The high hard water resistant hydraulic support concentrate according to claim 1 or 2, characterized in that: the particle size of the hydrophilic modified nano carbon microsphere is 400-500nm, and the specific surface area is 1000-1200m 2 The pore volume is 0.85-0.9mL/g, and the most probable pore diameter is 1.6-2.0nm.
4. The high hard water resistant hydraulic support concentrate of claim 1, wherein: the hydroxy cellulose is one or the combination of more than two of hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
5. The high hard water resistant hydraulic support concentrate of claim 1, wherein: the long-chain dibasic acid polyethylene glycol ester refers to dibasic acid polyethylene glycol ester containing more than 10 carbon atoms.
6. The high hard water resistant hydraulic support concentrate as defined in claim 5, wherein: the long-chain dibasic acid polyethylene glycol ester is one or the combination of more than two of sebacic acid polyethylene glycol 600 monoester, dodecanedioic acid polyethylene glycol 600 monoester, tridecanedioic acid polyethylene glycol 600 monoester and dimer acid polyethylene glycol 600 monoester.
7. The high hard water resistant hydraulic support concentrate of claim 1, wherein: the waterborne polyurethane is a two-component waterborne polyurethane containing-NCO group and-OH group in a molecular structure.
8. The high hard water resistant hydraulic support concentrate of claim 1, wherein: the weight percentage of the raw materials is as follows:
Figure FDA0003554603530000021
9. a method of preparing a hydraulic mount concentrate according to any one of claims 1 to 8, wherein: the method comprises the following steps:
(1) Adding 30% of water, monoethanolamine and waterborne polyurethane according to the proportion, and stirring for 10-30min at room temperature until the mixture is clear;
(2) Adding boric acid, caprylic acid, water-soluble polyvinyl alcohol, hydroxy cellulose, long-chain dibasic acid polyethylene glycol ester and ethylene glycol, heating to 60-80 ℃, adding the rest water, and stirring for 10-30min until the mixture is clear;
(3) Adding benzotriazole and hydrophilic modified nano carbon microspheres, stirring for 10-30min, and cooling to obtain the hydraulic support concentrated solution.
10. Use of the hydraulic mount concentrate of any one of claims 1-8 in a high hard water environment, wherein: the hardness of the hard water is 750-1500mg/L.
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