CN113173728B - Alkali-free accelerator for resisting aggregate alkali activity reaction and preparation method thereof - Google Patents
Alkali-free accelerator for resisting aggregate alkali activity reaction and preparation method thereof Download PDFInfo
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- CN113173728B CN113173728B CN202110500105.3A CN202110500105A CN113173728B CN 113173728 B CN113173728 B CN 113173728B CN 202110500105 A CN202110500105 A CN 202110500105A CN 113173728 B CN113173728 B CN 113173728B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/14—Hardening accelerators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application relates to the technical field of concrete additives, and discloses an alkali-free accelerator for resisting an aggregate alkali active reaction and a preparation method thereof, wherein raw materials comprise: the solution A comprises water, aluminum acid salt or hydroxide, organic or inorganic salts of calcium, iron, magnesium and lithium, and alcohol amine organic matters; the solution B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or derivatives thereof; mixing the solution A and the solution B in a mass ratio of 3-8:1. The alkali-free accelerator for resisting the aggregate alkali activity reaction prepared by the method has wide adaptability, can meet the requirement of setting time aiming at various cementing materials, can meet the requirement of dangerous rock support shotcrete, has quick setting time, has super early strength and quick strength increase.
Description
Technical Field
The application belongs to the technical field of concrete additives, and particularly relates to an alkali-free accelerator for resisting an aggregate alkali activity reaction and a preparation method thereof.
Background
The concrete accelerator is an additive which is mixed into concrete and can quickly harden the concrete. At present, the main types are powder accelerator prepared by mixing inorganic salts and liquid accelerator prepared by inorganic salts and organic substances. Accelerator is an indispensable additive in shotcrete construction methods. Their function is to accelerate the hydration hardening of the cement, forming sufficient strength in a very short time to guarantee the requirements of the particular construction. The accelerator is widely applied to the fields of railways, highways, ports, bridges, hydropower and the like, and makes outstanding contribution to the development of high-performance concrete in China.
In recent years, because wet-sprayed concrete has high construction efficiency and low rebound rate, construction environment is friendly and gradually replaces the traditional dry-sprayed concrete, liquid accelerator for wet-sprayed concrete comprises alkali accelerator and liquid alkali-free accelerator, and from the development of the liquid accelerator, the main problems of the alkali accelerator are as follows: high alkali content, large mixing amount, short stable period and 28d compressive strength ratio of less than 100%.
The existing alkali-free accelerator has the defects of slow setting time, low early strength and difficulty in meeting the construction requirement of sprayed concrete, and the traditional accelerator has the defect of poor durability when being applied to sprayed concrete, and has low anti-seepage and anti-cracking properties due to a plurality of holes in the sprayed concrete, so that the durability of the accelerator is reduced.
Disclosure of Invention
< technical problem to be solved by the application >
The method is used for solving the defects of slow setting time, low early strength and durability of the traditional alkali-free setting accelerator adopted by the current sprayed concrete.
< technical scheme adopted by the application >
Aiming at the technical problems, the application aims to provide an alkali-free accelerator for resisting the alkali activity reaction of aggregate.
The specific contents are as follows:
an alkali-free accelerator for resisting an aggregate alkali activity reaction, which comprises the following raw materials:
the solution A comprises water, aluminum acid salt or hydroxide, organic or inorganic salts of calcium, iron, magnesium and lithium, silicon-containing compounds and alcohol amine organic matters;
the solution B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or derivatives thereof;
mixing the solution A and the solution B in a mass ratio of 3-8:1.
< beneficial effects achieved by the application >
(1) The alkali-resistant accelerator has wide adaptability, can meet the requirement of setting time for various cementing materials, and can also meet the requirement of shotcrete for dangerous rock support.
(2) When the alkali-resistant accelerator is applied to sprayed concrete, the accelerator has quick setting time (1-10 min), super early strength and quick strength increase, and can reach 7.5MPa in 6 hours and 30.0MPa in 24 hours; the later strength is high, and the strength can be continuously improved.
(3) When the alkali-resistant accelerator is applied to sprayed concrete, the early strength is fast and high; the strength of 6h reaches more than 20% of the design strength, the design strength of 12h is 40%, the design strength of 24h is 60%, the design strength of 28d is 90%, and the design strength of 56d is more than 100%.
(3) When the alkali-resistant accelerator is applied to sprayed concrete, the workability of sprayed concrete (mortar) is greatly improved; compared with the traditional common sprayed concrete, the compactness is better, the pore diameter of the formed sprayed concrete is greatly reduced, and the mechanical impermeability and crack resistance of the sprayed concrete are obviously improved.
(4) When the alkali-resistant accelerator is applied to sprayed concrete, the rebound rate of sprayed concrete (mortar) is effectively reduced, compared with the rebound rate of traditional sprayed concrete (mortar) by more than 35-45%, the rebound rate is reduced to 4-8%, and the drop amplitude is more than 60%.
(5) When the alkali-resistant accelerator is applied to sprayed concrete, the durability is obviously improved, the main function of the traditional sprayed concrete (mortar) is that the dangerous rock is supported and reinforced, the durability is extremely poor or has serious influence, the holes are more, and the seepage resistance and crack resistance and the like are avoided. The sprayed concrete mortar added with the alkali-resistant accelerator can greatly improve the workability, remarkably improve the compactness of concrete, prevent the structure from generating volume shrinkage cracking, and greatly improve the impermeability and the cracking resistance.
(6) When the alkali-resistant accelerator is applied to sprayed concrete, the corrosion-resistant damage capability of the concrete can be improved. The components of the alkali-resistant accelerator react with tricalcium silicate, tricalcium aluminate, dicalcium silicate, tetracalcium aluminoferrite and other compounds in cement concrete to generate different micro-expansion crystals with stable crack resistance and densification performance, and the compounds of aluminum salt, calcium salt, lithium salt, phosphate and the like accelerate the rapid solidification of cement hydration. Besides meeting the initial and final time and mechanical properties, impermeability, crack resistance and freezing resistance of cement stone solidification, the cement can also be obviously improved to resist the erosion and damage of various acid and alkali ions (sulfate, carbonate, chloride and the like), and particularly can effectively prevent the reaction of potassium and sodium ions with alkali aggregates such as active silicon oxide, carbonate and the like in the aggregates, thereby having obvious effects on preventing and inhibiting the reaction of the alkali aggregates.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
First, the application provides an alkali-free accelerator for resisting an aggregate alkali active reaction, which comprises the following raw materials:
the solution A comprises water, aluminum acid salt or hydroxide, organic or inorganic salts of calcium, iron, magnesium and lithium, silicon-containing compounds and alcohol amine organic matters;
the solution B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or derivatives thereof;
mixing the solution A and the solution B in a mass ratio of 3-8:1.
In the application, the acid salt or hydroxide of aluminum comprises at least one of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum hydroxide; the silicon-containing compound includes at least one of ammonium silicate, or magnesium fluorosilicate.
In the present application, the organic or inorganic salts of calcium, iron, magnesium, and lithium include at least one of magnesium sulfate, magnesium nitrate, calcium nitrate, lithium phosphate, and lithium ferrate.
In the application, the alcohol amine comprises at least one of polymeric alcohol amine, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and diglycolamine.
In the present application, the small monomers include methacrylic acid and a polyol including polyethylene glycol or polyethylene triol.
In the present application, the sulfonate or its derivative includes at least one of lignin sulfonate and alpha-olefin sulfonate.
In the application, the reducing agent comprises at least one of vitamin C, sodium metabisulfite, sodium bisulphite, sodium hypophosphite and glucose,
the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate and azodiisobutyronitrile.
Secondly, the application provides a preparation method of an alkali-free accelerator for resisting an aggregate alkali active reaction, which comprises the following steps:
S1A liquid preparation
Adding water into a reaction kettle, adding aluminum acid salt or hydroxide, heating, continuously adding organic or inorganic salts of calcium, iron, magnesium and lithium and alcohol amine organic matters,
continuously stirring in the adding process until the adding object is dissolved, and cooling to normal temperature to obtain solution A;
S2B liquid preparation
Adding water into a reaction kettle, sequentially adding a mixture of acrylic acid and small monomers, a reducing agent, an initiator and a part of hypophosphite, continuously stirring and heating for reaction,
adding sulfonate or derivative thereof and the rest hypophosphite after the reaction is finished, stirring for reaction, and cooling to normal temperature to obtain solution B;
blending of S3A and B
And (3) mixing the solution A and the solution B in proportion, heating to 40-50 ℃, and carrying out heat preservation treatment to obtain the accelerator.
In the application, the liquid A and the liquid B are cooled to normal temperature and mixed in proportion for reaction, so that the liquid AB is subjected to crosslinking reaction, and the liquid AB is better, more uniform and stable than the conventional physical mixed system. In the application, 5 mass percent of 4-dimethylaminopyridine aqueous solution is dripped after the temperature is raised, the dripping time is 80min, and the adding amount of the 4-dimethylaminopyridine aqueous solution is 3-6%. The hydroxyl in the solution B and the compound in the solution A are subjected to complexation by the reaction of the solution AB to form a complex, the formed complex still can show the properties of the original two compounds, the complex also has an inhibitory effect on active aggregate in the concrete material, the durability of the concrete is enhanced, and after the reaction is completed, the high-performance alkali-resistant active sprayed concrete accelerator is obtained after cooling to normal temperature.
In the present application, the temperature is raised to 85℃in S1 and to 60℃in S2.
< example >
Example 1
An alkali-free accelerator for resisting the alkali activity reaction of aggregate, which is prepared by the following steps,
350kg of water and 350kg of aluminum sulfate are put into a reaction kettle A, and the temperature is raised to 85 ℃ and stirred for 0.5h until the aluminum sulfate is fully dissolved; 100kg of magnesium fluosilicate and 150kg of aluminum hydroxide are continuously added into the reaction kettle A, and stirring is continued until the magnesium fluosilicate and the aluminum hydroxide are completely dissolved, and stirring is carried out for about 0.5h. 50kg of magnesium sulfate, 60kg of lithium phosphate and 30kg of lithium ferrate are continuously added into the reaction kettle A, the mixture is stirred for 0.5h, 60kg of triethanolamine is continuously added, the mixture is stirred and reacted, and the mixture is kept warm for 20min after the solution is clarified. After the heat preservation is finished, cooling to normal temperature to obtain 1.5 tons of product A liquid.
300kg of water, 300kg of acrylic acid, 100kg of methacrylic acid, 70kg of polyethylene glycol, 5kg of ammonium persulfate, 1kg of vitamin C, 10kg of lithium hypophosphite, heating to 60 ℃, continuously reacting for 0.5h, continuously adding 200kg of alpha-olefin lithium sulfonate and 14kg of lithium hypophosphite, continuously stirring and reacting for 1.0h, and cooling to normal temperature to obtain 1.0 ton of product B.
Mixing and stirring the product A liquid and the product B liquid according to the mass ratio of 5:1, heating to 40-50 ℃, uniformly dripping 100kg of 5% mass fraction 4-dimethylaminopyridine aqueous solution, dripping 80min, preserving heat for 20min after the reaction is completed, and uniformly stirring to obtain the high-performance alkali-resistant active sprayed concrete accelerator.
Example 2
An alkali-free accelerator for resisting the alkali activity reaction of aggregate, which is prepared by the following steps,
adding 300kg of water and 350kg of aluminum sulfate into the reaction kettle A, heating to 85 ℃, and stirring for 0.5h until the aluminum sulfate is fully dissolved; 120kg of aluminum hydroxide, 30kg of calcium hydroxide and 100kg of ammonium silicate are continuously added into the reaction kettle A, and stirring is continued until the aluminum hydroxide and the calcium hydroxide are completely dissolved, and stirring is carried out for about 0.5h. 120kg of magnesium sulfate, 20kg of lithium oxalate and stirring for about 0.5h were continuously added into the reaction kettle A. 60kg of polyalcohol amine is continuously added, the mixture is stirred and reacted, after the solution is uniform and the temperature is kept for 20min, the mixture is cooled to normal temperature, and 1.5 tons of product A is obtained.
330kg of water, 270kg of acrylic acid, 100kg of methacrylic acid, 70kg of polyglycerol, 5kg of ammonium persulfate, 1kg of vitamin C, 10kg of ammonium hypophosphite, heating to 60 ℃, continuously reacting for 0.5h, continuously adding 200kg of alpha-olefin lithium sulfonate and 14kg of ammonium hypophosphite, continuously stirring and reacting for 1.0h, and cooling to normal temperature to obtain 1.0 ton of product B.
Mixing and stirring the product A liquid and the product B liquid according to the mass ratio of 6:1, heating to 40-50 ℃, uniformly dripping 100kg of 5% mass fraction 4-dimethylaminopyridine aqueous solution, dripping 80min, preserving heat for 20min after the reaction is finished, and uniformly stirring to obtain the high-performance alkali-resistant active shotcrete accelerator.
Example 3
The difference between this example and example 1 is that the mass ratio of liquid A to liquid B is 3:1.
Example 4
The difference between this example and example 1 is that the mass ratio of liquid A to liquid B is 8:1.
Example 5
This example differs from example 1 in that no aqueous solution of 4-dimethylaminopyridine was added.
Comparative example
Comparative example 1
The comparative example differs from example 1 in that liquid B was not added.
Comparative example 2
The difference between this comparative example and example 1 is that the mass ratio of liquid A to liquid B is 2:1.
Comparative example3
The difference between this comparative example and example 1 is that the mass ratio of liquid A to liquid B is 9:1.
< test example >
The performance of the accelerator prepared in examples 1-5 and comparative examples 1-3 was measured, and the results showed that examples 1-5 all meet the relevant standards of GB/T35159-2017 accelerator for shotcrete.
Standard tests were performed on the above samples (example 1, examples 3-5, comparative examples 1-3), and the test results are shown in Table 1.
Table 1 test results
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (3)
1. An alkali-free accelerator for resisting aggregate alkali activity reaction, which is characterized in that the raw materials comprise:
the solution A comprises water, aluminum acid salt or hydroxide, organic or inorganic salts of calcium, iron, magnesium and lithium, silicon-containing compounds and alcohol amine organic matters;
the solution B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or derivatives thereof;
mixing the solution A and the solution B in a mass ratio of 3-8:1;
the acid salt or hydroxide of aluminum comprises at least one of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum hydroxide; the silicon-containing compound includes at least one of ammonium silicate, or magnesium fluorosilicate;
the organic or inorganic salts of calcium, iron, magnesium and lithium comprise at least one of magnesium sulfate, magnesium nitrate, calcium nitrate, lithium phosphate and lithium ferrate;
the alcohol amine comprises at least one of polymeric alcohol amine, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and diglycolamine;
the small monomers comprise methacrylic acid and polyalcohol, and the polyalcohol comprises polyethylene glycol or polyethylene triol;
the sulfonate or the derivative thereof comprises at least one of lignin sulfonate and alpha-olefin sulfonate;
the reducing agent comprises at least one of vitamin C, sodium metabisulfite, sodium bisulphite, sodium hypophosphite and glucose, and the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate and azodiisobutyronitrile.
2. A method for preparing the alkali-free accelerator for resisting the alkali-activated reaction of aggregate according to claim 1, comprising the following steps:
S1A liquid preparation
Adding water into a reaction kettle, adding aluminum acid salt or hydroxide, heating, continuously adding organic or inorganic salts of calcium, iron, magnesium and lithium, silicon-containing compounds and alcohol amine organic matters,
continuously stirring in the adding process until the adding object is dissolved, and cooling to normal temperature to obtain solution A;
S2B liquid preparation
Adding water into a reaction kettle, sequentially adding a mixture of acrylic acid and small monomers, a reducing agent, an initiator and a part of hypophosphite, continuously stirring and heating for reaction,
adding sulfonate or derivative thereof and the rest hypophosphite after the reaction is finished, stirring for reaction, and cooling to normal temperature to obtain solution B;
blending of S3A and B
Mixing the solution A and the solution B in proportion, heating to 40-50 ℃, and performing heat preservation treatment to obtain an accelerator;
after heating, dropwise adding 5% of 4-dimethylaminopyridine aqueous solution in mass fraction for 80min, wherein the addition amount of the 4-dimethylaminopyridine aqueous solution is 3-6%.
3. The method for preparing alkali-free accelerator for alkali-resistant reaction of aggregate according to claim 2, wherein the temperature is raised to 85 ℃ in S1 and to 60 ℃ in S2.
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