CN112852534A - Mine support solution and preparation method thereof - Google Patents
Mine support solution and preparation method thereof Download PDFInfo
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- CN112852534A CN112852534A CN202110099152.1A CN202110099152A CN112852534A CN 112852534 A CN112852534 A CN 112852534A CN 202110099152 A CN202110099152 A CN 202110099152A CN 112852534 A CN112852534 A CN 112852534A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
- C10M149/18—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2217/044—Polyamides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
Abstract
The invention provides a mine support solution and a preparation method thereof. The mine support solution comprises: polyamide mixture, antirust agent, anionic surfactant, nonionic surfactant, lubricant, pH regulator, defoaming agent and soft water; the polyamide mixture comprises polyamide obtained by reacting at least one organic acid compound and at least one polyamine compound. The invention reasonably compounds various organic additives which are easy to biodegrade, so that the product has good lubricating property and good protectiveness to the interior of a cylinder body which is made of ferrous metal in a hydraulic support, a valve element and a valve core which are made of galvanized materials and the like.
Description
Technical Field
The invention belongs to the technical field of hydraulic support solutions, and particularly relates to a mine support solution and a preparation method thereof.
Background
The mine hydraulic support is widely applied to the comprehensive mechanized coal mining working face of a coal mine, and working liquid of the mine hydraulic support is high-water-content hydraulic liquid obtained by diluting emulsified oil or concentrated liquid which is mine support liquid with water. Nitrite is widely used in mine scaffolding fluid as an inexpensive rust inhibitor, and reacts with secondary amine to produce nitrosamine having carcinogenicity, and the european union has clearly banned nitrite from being used in industrial oil. Mineral oil is generally added into a large class of emulsified oil products in mine support liquid to serve as a lubricating carrier. According to the test method of OECD301C, the biodegradability of mineral oil in a 28-day test period is less than 20%, and the lower limit value of 60% which can not meet the requirement of rapid biodegradation is far from being met. However, due to the harsh underground environment, the hydraulic fluid leaks and then directly enters the soil, and the added nitrite and mineral oil can cause serious pollution to the soil and underground water sources.
The valve core of the valve of the hydraulic support is made of zinc plating besides common alloy steel, and the zinc plating process is widely used as ferrous metal of a sacrificial anode protection substrate. The nitrite used as the antirust agent has strong oxidizability, zinc is easily oxidized into zinc oxide to fall off, and the oxidized zinc layer falls off and then enters the hydraulic fluid, so that the blockage of a valve core of the valve and the leakage of the hydraulic fluid are easily caused; after the fallen coating enters the hydraulic system, the filter is easy to block, and the hydraulic system works abnormally.
CN108219911A discloses a concentrated solution for a fully synthetic hydraulic support and a preparation method thereof, wherein the concentrated solution comprises the following components in percentage by weight: 5-15% of composite antirust preservative, 2-6% of lubricant, 3-8% of organic alcohol amine, 5-15% of surfactant, 3-15% of hard water resisting agent and 50-75% of softened water. The hydraulic support concentrated solution has good stability, but the zinc protection capability of the hydraulic support concentrated solution needs to be improved.
CN108485772A discloses a green environmental-friendly mine hydraulic support liquid, which comprises mineral base oil and an additive, wherein the additive comprises the following components: 3-30 parts of mineral base oil, 2-15 parts of fatty acid, 0-10 parts of alkylamine, 1-5 parts of diethylene glycol monobutyl ether, 2-20 parts of emulsifier, 0.1-0.8 part of antirust agent, 0-12 parts of EDTA tetrasodium, 0-8 parts of alcohol amine, 2-15 parts of water-based antirust agent, 0.1-1.0 part of sodium hydroxide, 0.1-3 parts of bactericide, 0.01-0.8 part of defoaming agent and water. The mineral base oil is added as a lubricating carrier, but the biodegradability of the mineral base oil is extremely poor, and the mineral base oil can cause serious pollution to soil and underground water sources.
CN109777582A discloses a green and environment-friendly biodegradable mine hydraulic support solution and a preparation method thereof, wherein the green and environment-friendly biodegradable mine hydraulic support solution comprises 70-97 parts by weight of an additive and 30-3 parts by weight of animal and vegetable oil, the additive comprises 2-15 parts by weight of a water-based antirust agent, 2-15 parts by weight of fatty acid, 0-10 parts by weight of alkylamine, 1-5 parts by weight of ethylene glycol monobutyl ether, 2-20 parts by weight of an emulsifier, 0.1-0.8 part by weight of an antirust agent, 0-12 parts by weight of tetrasodium EDTA, 1-8 parts by weight of alcohol amine, 0.1-1.0 part by weight of sodium hydroxide, 0.1-3 parts by weight of a bactericide, 0.01-0.8 part by weight of a defoaming agent and 88.69-6.4 parts by weight of water, and the animal and vegetable oil is added as a lubricating carrier, so that although the zinc protection capability is biodegradable, the zinc protection.
Therefore, the development of a mine hydraulic support fluid with good lubricating property and good protection property is the focus of research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a mine support solution and a preparation method thereof. The mine support solution does not contain nitrite, mineral oil, zinc and good biodegradability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a mine scaffolding fluid comprising: polyamide mixture, antirust agent, anionic surfactant, nonionic surfactant, lubricant, pH regulator, defoaming agent and soft water;
the polyamide mixture comprises polyamide obtained by reacting at least one organic acid compound and at least one polyamine compound.
In the invention, a polyamide mixture formed by reacting at least one organic acid compound and at least one polyamine compound is added, and the polyamide mixture prepared by carrying out amidation reaction on organic carboxylic acid with different carbon chain lengths and functionalities and the polyamine compound can replace nitrite to be used as an antirust agent and has good protection on ferrous metals. Meanwhile, the galvanized part can be well protected by adjusting the pH buffer system; the mine support liquid has the advantages that the non-ionic surfactant, the anionic surfactant, the lubricant, the defoaming agent and the antirust agent are introduced, the components are matched with each other and have synergistic interaction, so that the mine support liquid has excellent antirust performance and better lubricity, and after the non-ionic surfactant is introduced, a polyamide mixture can be uniformly dispersed in a hard water system without generating a soap precipitation phenomenon.
Preferably, the mine support solution comprises the following components in percentage by mass: 15-35% of polyamide mixture, 0.1-0.8% of antirust agent, 0.2-1.3% of anionic surfactant, 0.2-1.5% of nonionic surfactant, 1.0-4.5% of lubricant, 0.5-3.0% of pH regulator, 0.02-0.1% of defoaming agent and the balance of soft water.
The content of the polyamide mixture may be 15 to 35%, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, or the like, based on 100% by mass of the total mine-supporting fluid.
The content of the rust inhibitor is 0.1 to 0.8%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or the like, based on 100% by mass of the total mine-supporting fluid.
The content of the anionic surfactant is 0.2 to 1.3% by mass of the total amount of the mine-supporting liquid as 100%, and may be, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, or the like.
The content of the nonionic surfactant is 0.2 to 1.5% by mass of the total amount of the mine support solution as 100%, and may be, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, or the like.
The content of the lubricant is 1.0 to 4.5% based on 100% of the total mass of the mine support solution, and may be, for example, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.5%, or the like.
The content of the pH adjuster is 0.5 to 3.0% based on 100% of the total mass of the mine scaffolding fluid, and may be, for example, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, or the like.
The content of the defoaming agent is 0.02 to 0.1%, for example, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, or the like, based on 100% by mass of the total mine support fluid.
Preferably, the organic acid compound is a monoacid and/or a polyacid.
Preferably, the monoacid is selected from C8-C12 (for example, C8, C9, C10, C11 and C12) saturated monoacids and/or C12-C18 (for example, C12, C13, C14, C15, C16, C17 and C18) unsaturated fatty acids, preferably any one or a combination of at least two of caprylic acid, capric acid, caprylic-capric acid, oleic acid and tall oil acid.
Preferably, the polybasic acid is a dibasic acid, preferably any one or a combination of at least two of adipic acid, sebacic acid, azelaic acid or C18-C22 (which may be, for example, C18, C19, C20, C21, C22) dimer acid.
In the invention, because the dibasic acid has two carboxyl groups, the molecular weight of the polyamide and the number of the amide functional groups can be effectively improved through chain extension in the reaction process, the adsorption capacity of the polyamide on the metal surface is improved, and the excellent antirust property is further shown. Meanwhile, as the molecular weight is increased, the lubricity is improved, and the lubricating oil is indispensable in polyamide mixtures.
Preferably, the polyamine compound is selected from one of or a combination of at least two of tetraethylenepentamine, triethylene tetramine, pentaethylenehexamine and polyethylene polyamine.
Preferably, the antirust agent is selected from any one or a combination of at least two of benzotriazole, methyl benzotriazole, benzotriazole derivatives, N- [ (5-methyl-1H-benzotriazole-1-yl) methyl ] diethanolamine or dimercaptothiadiazole salts, and is preferably benzotriazole.
Preferably, the anionic surfactant is any one or a combination of at least two of C8-C18 (for example, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 and C18) fatty alcohol polyoxyethylene ether carboxylic acid.
In the invention, the reason why the C8-C18 fatty alcohol polyoxyethylene ether carboxylic acid is selected as the anionic surfactant is as follows: the coal mine water has large fluctuation of water hardness, the general content of calcium and magnesium ions is high, and the surfactant can well disperse the calcium and magnesium ions and prevent calcium and magnesium soap from precipitating; but also plays a role in emulsification assistance.
Preferably, the nonionic surfactant is one or a combination of at least two of isomeric dodecyl alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether or isomeric pentadecanol polyoxyethylene ether, and is preferably isomeric tridecanol polyoxyethylene ether.
In the present invention, the reason why the isomeric tridecanol polyoxyethylene ether is selected as the nonionic surfactant is that: the emulsifying agent has strong emulsifying capacity.
Preferably, the lubricant is an ethoxypropoxy copolymer.
In the present invention, the reason why the ethoxypropoxy copolymer is selected as the lubricant is that: the lubricant has good biodegradability and low foam.
Preferably, the weight average molecular weight of the ethoxypropoxy copolymer is 80000 to 120000, and may be, for example, 80000, 85000, 90000, 95000, 100000, 105000, 110000, 115000, 120000, or the like.
Preferably, the pH adjusting agent is selected from any one or a combination of at least two of monoethanolamine, triethanolamine or isopropanolamine.
Preferably, the pH of the mine scaffolding fluid is 9.0-9.5, and may be, for example, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, and the like.
Preferably, the defoamer is a silicone-based defoamer.
In a second aspect, the present invention provides a method of preparing a mine scaffolding fluid as defined in the first aspect, the method comprising the steps of:
(1) mixing an organic acid compound and a polyamine compound, heating for reaction, and mixing with part of soft water after the reaction is finished to obtain a polyamide mixture;
(2) and (2) mixing the polyamide mixture obtained in the step (1) with a rust inhibitor, an anionic surfactant, a nonionic surfactant, a lubricant, a pH regulator, a defoaming agent and the rest of soft water to obtain the mine support solution.
Preferably, in the step (1), the temperature of the temperature-raising reaction is 140 to 160 ℃, for example, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃ and the like, and the time of the temperature-raising reaction is 1 to 3 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours and the like.
Preferably, in step (1), after the reaction is completed, the acid value of the obtained polyamide mixture is 0-45 mgKOH/g, and may be, for example, 0KOH/g, 1KOH/g, 2KOH/g, 4KOH/g, 6KOH/g, 8KOH/g, 10KOH/g, 15KOH/g, 20KOH/g, 25KOH/g, 30KOH/g, 35KOH/g, 40KOH/g, 45KOH/g, or the like.
Preferably, the mass ratio of the part of the soft water in the step (1) to the soft water remaining in the step (2) is (1-1.5):1, and may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and the like.
Preferably, in the step (2), the additive adding step specifically comprises: and (2) adding an antirust agent into the polyamide mixed solution obtained in the step (1), stirring until solid particles are completely dissolved, sequentially adding an anionic surfactant, a nonionic surfactant and a lubricant, uniformly stirring, adding the rest soft water, adding a pH regulator to adjust the pH value, finally adding a defoaming agent, and stirring until the product is transparent and uniform.
Preferably, in the step (2), the temperature of the polyamide mixed solution is reduced to 40-50 ℃ (for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃ and the like) and then the antirust agent is added.
Compared with the prior art, the invention has the following beneficial effects:
(1) the mine support solution disclosed by the invention has good lubricating property and good protection property for the interior of a cylinder body made of ferrous metal and a valve element and a valve core made of galvanized materials in a hydraulic support through reasonably compounding various organic additives which are easy to biodegrade;
(2) according to the test of OECD301E, the biodegradability of the mine support liquid reaches over 85% in 28 days.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the components in the following examples are as follows: c8 unsaturated alcohol polyoxyethylene ether carboxylic acid is available from KAO Chemicals Gmbh, C18 unsaturated alcohol polyoxyethylene ether carboxylic acid is available from KAO Chemicals Gmbh, isomeric dodecanol polyoxyethylene ether is available from Sasol (China) chemical Co., Ltd, isomeric tridecanol polyoxyethylene ether is available from Sasol (China) chemical Co., Ltd, ethoxypropoxy copolymer is available from Pastef China Co., Ltd, and siloxane defoamer is available from Si 555.
Example 1
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution specifically comprises the following steps:
(1) sequentially adding tetraethylenepentamine, triethylene tetramine, caprylic acid and adipic acid into a reaction kettle, fully and uniformly mixing, slowly raising the temperature to 150 ℃, removing water generated in the reaction, continuously reacting for 2 hours, adding soft water after the acid value is qualified, and cooling to obtain a polyamide mixture;
(2) and (3) when the temperature is reduced to 45 ℃, adding an antirust agent, stirring until solid particles are completely dissolved, sequentially adding an anionic surfactant, a nonionic surfactant and a lubricant, uniformly stirring, adding the rest soft water, adding a pH regulator to adjust the pH value to 9.2, adding an antifoaming agent, and stirring until the product is transparent and uniform to obtain the mine support liquid.
Example 2
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution specifically comprises the following steps:
(1) sequentially adding tetraethylenepentamine, triethylene tetramine, caprylic acid and adipic acid into a reaction kettle, fully and uniformly mixing, slowly raising the temperature to 150 ℃, removing water generated in the reaction, continuously reacting for 2 hours, adding soft water after the acid value is qualified, and cooling to obtain a polyamide mixture;
(2) and (3) when the temperature is reduced to 45 ℃, adding an antirust agent, stirring until solid particles are completely dissolved, sequentially adding an anionic surfactant, a nonionic surfactant and a lubricant, uniformly stirring, adding the rest soft water, adding a pH regulator to adjust the pH value to 9.4, adding an antifoaming agent, and stirring until the product is transparent and uniform to obtain the mine support liquid.
Example 3
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution in this example is the same as that in example 1.
Example 4
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution in this example is the same as that in example 1.
Example 5
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution in this example is the same as that in example 1.
Example 6
The embodiment provides a mine support solution, which comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation raw materials of the polyamide mixture comprise the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
the preparation method of the mine support solution in this example is the same as that in example 1.
Example 7
This example provides a mine scaffolding fluid which differs from example 1 only in that adipic acid is replaced with an equivalent mass of suberic acid, and the contents of other components and preparation method are the same as in example 1.
Example 8
This example provides a mine scaffolding fluid which differs from example 1 only in that no octanoic acid is added, the adipic acid content is increased to 28.3%, and the other component contents and preparation method are the same as example 1.
Example 9
This example provides a mine scaffolding fluid which differs from example 1 only in that tetraethylenepentamine is not added, the triethylene tetramine content is increased to 26.7% (based on 100% by mass of the polyamide mixture), and the other component contents and preparation method are the same as example 1.
Example 10
This example provides a mine scaffolding fluid which differs from example 1 only in that, without the addition of triethylenetetramine, the tetraethylenepentamine content is increased to 26.7% (based on 100% by mass of the polyamide mixture), and the other component contents and preparation method are the same as example 1.
Example 11
This example provides a mine scaffolding fluid, which differs from example 1 only in that C18 unsaturated alcohol polyoxyethylene ether carboxylic acid is replaced with equal mass of C8 unsaturated alcohol polyoxyethylene ether carboxylic acid, and the contents of other components and preparation method are the same as example 1.
Example 12
The present example provides a mine support solution, which is different from example 1 only in that isomeric tridecanol polyoxyethylene ether is replaced by isomeric tridecanol polyoxyethylene ether with equal mass, and the contents of other components and the preparation method are the same as example 1.
Comparative example 1
The comparative example provides a mine support solution, and the mine support solution comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
| components | Mass percent/% of |
| Sodium nitrite | 9 |
| Sebacic acid | 2.1 |
| Oleic acid | 2.8 |
| Ethanolamine | 4.2 |
| Triethanolamine | 1.0 |
| Benzotriazole | 0.5 |
| C18 unsaturated alcohol polyoxyethylene ether carboxylic acid | 0.5 |
| Isomeric tridecanol polyoxyethylene ether | 1.0 |
| Potassium hydroxide | 1.8 |
| Siloxane-based defoaming agent | 0.05 |
| Soft water | Supplement to 100 |
The preparation method of the mine support solution comprises the following steps: adding part of soft water, sequentially adding monoethanolamine, triethanolamine and potassium hydroxide, uniformly stirring, adding benzotriazole, after the solid is completely dissolved, sequentially adding sebacic acid, oleic acid, C18 unsaturated alcohol polyoxyethylene ether carboxylic acid, isomeric tridecanol polyoxyethylene ether and sodium nitrite, stirring until the mixture is clear and transparent, adding the rest of soft water and siloxane defoamer, and uniformly stirring.
Comparative example 2
The comparative example provides a mine support solution, and the mine support solution comprises the following components in percentage by mass based on 100% of the mass of the mine support solution:
the preparation method of the mine support solution comprises the following steps: adding part of soft water, sequentially adding monoethanolamine and triethanolamine, stirring uniformly, adding benzotriazole, after the solid is completely dissolved, sequentially adding oleic acid, isotridecanol polyoxyethylene ether and sodium sulfonate, stirring uniformly, adding mineral oil, stirring for clarification, adding sodium nitrite, stirring until the solid is dissolved, adding the rest of soft water and siloxane defoamer, and stirring uniformly.
Comparative example 3
The comparative example provides a mine support solution, which is different from the mine support solution in example 1 only in that a polyamine compound is replaced by a monoamine compound, namely the preparation raw material of the polyamide mixture comprises the following components in percentage by mass based on 100% of the mass of the polyamide mixture:
comparative example 4
This comparative example provides a mine scaffolding fluid which differs from example 1 only in that the anionic surfactant (C18 unsaturated alcohol polyoxyethylene ether carboxylic acid) is not added, the content of the nonionic surfactant (isotridecanol polyoxyethylene ether) is increased to 2.1%, and the content of other components and the preparation method are the same as example 1.
Comparative example 5
This comparative example provides a mine scaffolding fluid which differs from example 1 only in that the nonionic surfactant (isomeric tridecanol polyoxyethylene ether) is not added, but the anionic surfactant (C18 unsaturated alcohol polyoxyethylene ether carboxylic acid) content is increased to 2.1%, and the other component contents and preparation method are the same as example 1.
Performance testing
The mine scaffold fluids provided in the above examples 1 to 12 and comparative examples 1 to 5 were subjected to the following performance tests, in which the specific test methods refer to MT 76-2011 Standard test of emulsified oil, concentrated solution and high-water-content hydraulic fluid for Hydraulic scaffolds, and refer to BOD for wastewater treatment5/COD>0.3 has better biodegradability as an initial judgment basis, and the final biodegradability is tested according to the OECD301E test method;
the specific test results are shown in table 1, table 1 (the test items corresponding to the table numbers are consistent with table 1) and table 2 below, where "√" represents a test pass:
TABLE 1
TABLE 1
TABLE 2
The tests in the table show that: the mine support solution is transparent and uniform fluid and has no pungent smell; kinematic viscosity at 40 ℃ of 2.3-5.0mm2The condensation point is-13 to-10 ℃ without flash point; freeze-thaw resistance: 5 cycles, recovering the original state; uniformly dispersing in water; the pH value is 9.0-9.5; thermal stability: no precipitate, no floccule, no layering and no water precipitation are generated on the liquid surface; stability at room temperature: no precipitate, no floccule, no layering and no water precipitation are generated on the liquid surface; oscillation stability: the cast iron has no rust or color change; antirust property: the cast iron has no rust or color change; corrosion resistance: no. 15 steel bar is not rusted, and No. 62 brass bar is not discolored and corroded; the volume of the defoaming residual foam is 0-2 mL; the refractometer has a scale number of 1.2-1.4.
In particular, example 1 showed a biodegradability of 87.7% after 28 days according to the OECD301E test, meeting the requirement of rapid biodegradability.
The applicant states that the invention is illustrated by the above examples of the mine support solution and the preparation method thereof, but the invention is not limited to the above examples, i.e. it is not meant that the invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A mine scaffolding fluid, comprising: polyamide mixture, antirust agent, anionic surfactant, nonionic surfactant, lubricant, pH regulator, defoaming agent and soft water;
the polyamide mixture comprises polyamide obtained by reacting at least one organic acid compound and at least one polyamine compound.
2. The mine scaffolding fluid according to claim 1, wherein the mine scaffolding fluid comprises, in mass%: 15-35% of polyamide mixture, 0.1-0.8% of antirust agent, 0.2-1.3% of anionic surfactant, 0.2-1.5% of nonionic surfactant, 1.0-4.5% of lubricant, 0.5-3.0% of pH regulator, 0.02-0.1% of defoaming agent and the balance of soft water.
3. The mine scaffolding fluid according to claim 1 or 2, wherein the organic acid-based compound is a mono-acid and/or a poly-acid;
preferably, the monoacid is selected from C8-C12 saturated monoacids and/or C12-C18 unsaturated fatty acids, preferably any one or a combination of at least two of caprylic acid, capric acid, caprylic-capric acid, oleic acid or tall oil acid;
preferably, the polybasic acid is dibasic acid, preferably any one or a combination of at least two of adipic acid, sebacic acid, azelaic acid or C18-C22 dimer acid;
preferably, the polyamine compound is selected from one of or a combination of at least two of tetraethylenepentamine, triethylene tetramine, pentaethylenehexamine and polyethylene polyamine.
4. The mine scaffolding fluid according to any one of claims 1 to 3, wherein the rust inhibitor is selected from any one or a combination of at least two of benzotriazole, tolyltriazole, a benzotriazole derivative, N- [ (5-methyl-1H-benzotriazol-1-yl) methyl ] diethanolamine or a dimercaptothiadiazole salt, preferably benzotriazole.
5. The mine support fluid of any one of claims 1 to 4, wherein the anionic surfactant is any one or a combination of at least two of C8-C18 fatty alcohol-polyoxyethylene ether carboxylic acids, preferably C18 fatty alcohol-polyoxyethylene ether carboxylic acid;
preferably, the nonionic surfactant is one or a combination of at least two of isomeric dodecyl alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether or isomeric pentadecanol polyoxyethylene ether, and is preferably isomeric tridecanol polyoxyethylene ether.
6. The mine scaffolding fluid of any one of claims 1 to 5, wherein the lubricant is an ethoxypropoxy copolymer;
preferably, the weight average molecular weight of the ethoxy propoxy copolymer is 80000-120000.
7. The mine scaffolding fluid of any one of claims 1 to 6, wherein the pH adjuster is selected from any one or a combination of at least two of monoethanolamine, triethanolamine or isopropanolamine;
preferably, the pH of the mine scaffolding fluid is 9.0-9.5;
preferably, the defoamer is a silicone-based defoamer.
8. The method of preparing a mine scaffolding fluid according to any one of claims 1 to 7, wherein the method of preparing the mine scaffolding fluid includes the steps of:
(1) mixing an organic acid compound and a polyamine compound, heating for reaction, and mixing with part of soft water after the reaction is finished to obtain a polyamide mixture;
(2) and (2) mixing the polyamide mixture obtained in the step (1) with a rust inhibitor, an anionic surfactant, a nonionic surfactant, a lubricant, a pH regulator, a defoaming agent and the rest of soft water to obtain the mine support solution.
9. The preparation method of the mine support solution according to claim 8, wherein in the step (1), the temperature of the temperature-raising reaction is 140-160 ℃, and the time of the temperature-raising reaction is 1-3 hours;
preferably, in the step (1), after the reaction is completed, the acid value of the obtained polyamide mixture is 0-45 mgKOH/g;
preferably, the mass ratio of the part of the soft water in the step (1) to the soft water remaining in the step (2) is (1-1.5): 1.
10. The preparation method of the mine support fluid according to claim 8 or 9, wherein in the step (2), the additive adding step is specifically: adding an antirust agent into the polyamide mixed solution obtained in the step (1), stirring until solid particles are completely dissolved, sequentially adding an anionic surfactant, a nonionic surfactant and a lubricant, uniformly stirring, adding the rest soft water, adding a pH regulator to adjust the pH value, finally adding a defoaming agent, and stirring until the product is transparent and uniform;
preferably, in the step (2), the temperature of the polyamide mixed solution is reduced to 40-50 ℃, and then the antirust agent is added.
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