CN113173728A - Alkali-free accelerator resisting aggregate alkali activity reaction and preparation method thereof - Google Patents
Alkali-free accelerator resisting aggregate alkali activity reaction and preparation method thereof Download PDFInfo
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- CN113173728A CN113173728A CN202110500105.3A CN202110500105A CN113173728A CN 113173728 A CN113173728 A CN 113173728A CN 202110500105 A CN202110500105 A CN 202110500105A CN 113173728 A CN113173728 A CN 113173728A
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- alkali
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- free accelerator
- resisting
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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
-
- 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
Abstract
The invention relates to the technical field of concrete admixtures, and discloses an alkali-free accelerator resisting the alkali activity reaction of aggregates and a preparation method thereof, wherein the alkali-free accelerator comprises the following raw materials: the liquid A comprises water, an acid salt or hydroxide of aluminum, organic salt or inorganic salt of calcium, iron, magnesium and lithium and an alcamines organic matter; the liquid B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or a derivative thereof; mixing the solution A and the solution B according to the mass ratio of 3-8: 1. The alkali-free setting accelerator capable of resisting the alkali activity reaction of the aggregate prepared by the application has wide adaptability, can meet the setting time requirement aiming at various cementing materials, can also meet the requirement of sprayed concrete for dangerous rock support, has quick setting time, super early strength and quick strength increase.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to an alkali-free accelerator resisting the alkali activity reaction of aggregates and a preparation method thereof.
Background
The concrete accelerator is an additive which is added into concrete and can make the concrete quickly set and harden. At present, the main types are powder accelerators prepared by mixing inorganic salts and liquid accelerators prepared by mixing inorganic salts and organic substances. The accelerator is an indispensable additive in the concrete spraying construction method. Their function is to accelerate the hydration hardening of the cement and to develop 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, as wet shotcrete has high construction efficiency, low resilience and friendly construction environment, the tendency of gradually replacing the traditional dry shotcrete is existed, liquid setting accelerators for the wet shotcrete comprise an alkali setting accelerator and a liquid alkali-free setting accelerator, and from the development of the liquid setting accelerators, the main problems existing in the alkali setting accelerators are as follows: high alkali content, large mixing amount, short stabilization period and 28d compressive strength ratio of less than 100 percent.
The prior alkali-free accelerator has the defects of slow accelerating time, low early strength and difficulty in meeting the construction requirements of sprayed concrete, and the traditional accelerator has the defect of poor durability when being applied to the sprayed concrete, and the durability of the sprayed concrete is reduced due to the fact that a plurality of holes are formed in the sprayed concrete and the impermeability and crack resistance are poor.
Disclosure of Invention
< problems to be solved by the present invention >
The quick-setting agent is used for overcoming the defects of slow quick-setting time, low early strength and durability of the conventional alkali-free quick-setting agent adopted by the conventional sprayed concrete.
< technical solution adopted in the present invention >
In view of the above technical problems, the present invention aims to provide an alkali-free setting accelerator for resisting the alkali activity reaction of aggregates.
The specific contents are as follows:
an alkali-free accelerator for resisting the alkali activity reaction of aggregate, which comprises the following raw materials:
the liquid A comprises water, an acid salt or hydroxide of aluminum, organic salt or inorganic salt of calcium, iron, magnesium and lithium, a silicon-containing compound and an alcamines organic matter;
the liquid B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or a derivative thereof;
mixing the solution A and the solution B according to the mass ratio of 3-8: 1.
< advantageous effects achieved by the present invention >
(1) The alkali-resistant accelerator has wide adaptability, can meet the setting time requirement aiming at various cementing materials, and can also meet the requirement of sprayed concrete for dangerous rock support.
(2) When the alkali-resistant accelerator is applied to sprayed concrete, the quick setting time is fast (1-10 min), the early strength is achieved, the strength is increased fast, 7.5MPa can be achieved within 6 hours, and 30.0MPa can be achieved within 24 hours; later stage intensity is high, can last lifting strength.
(3) When the alkali-resistant accelerator is applied to sprayed concrete, the ultra-early strength is high; the strength of 6h reaches more than 20 percent of the designed strength, 12h is more than 40 percent of the designed strength, 24h is more than 60 percent of the designed strength, 28d is more than 90 percent of the designed strength, and 56d is more than 100 percent of the designed strength.
(3) When the alkali-resistant accelerator is applied to sprayed concrete, the workability of the sprayed concrete (mortar) is greatly improved; compared with the traditional common sprayed concrete, the compactness is better, the pore diameters of the holes, the holes and the pore channels of the formed sprayed concrete are greatly reduced, and the mechanical impermeability and the crack resistance of the sprayed concrete are obviously improved.
(4) The alkali-resistant accelerator is applied to sprayed concrete, effectively reduces the rebound rate of sprayed concrete (mortar), reduces the rebound rate to 4-8% and reduces the reduction range to be more than 60% compared with the traditional sprayed concrete (mortar) with the rebound rate of more than 35-45%.
(5) When the alkali-resistant accelerator is applied to sprayed concrete, the durability is remarkably improved, the main function of the traditional sprayed concrete (mortar) is support and reinforcement of dangerous rocks, the durability is extremely poor or seriously affected, and the alkali-resistant accelerator has many holes, does not have impermeability and crack resistance and the like. The sprayed concrete mortar added with the alkali-resistant accelerator can greatly improve the workability, obviously improve the compactness of concrete, prevent structures from generating volume shrinkage cracking easily, and greatly improve the impermeability and crack resistance of the structures.
(6) The application of the alkali-resistant accelerator for the sprayed concrete can improve the corrosion resistance and destruction resistance of the concrete. The components of the alkali-resistant accelerator react with compounds such as tricalcium silicate, tricalcium aluminate, dicalcium silicate and tetracalcium aluminoferrite in cement concrete in a hydration mode to generate different types of micro-expansion crystals with stable anti-cracking compact performance and compounds such as aluminum salt, calcium salt, lithium salt and phosphate for accelerating hydration, rapid setting and curing of cement. Besides meeting the requirements of initial and final curing time and mechanical properties, impermeability, crack resistance and frost resistance of the set cement, the cement can also obviously improve the resistance of the cement to the erosion damage of various acid and alkali ions (sulfate, carbonate, chloride and the like), and particularly can effectively prevent potassium nano ions from reacting with alkali aggregates such as active silicon oxide, carbonate and the like in the aggregates, thereby having obvious effects on preventing and inhibiting the alkali aggregate reaction.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides an alkali-free accelerator for resisting the alkali activity reaction of aggregate, which comprises the following raw materials:
the liquid A comprises water, an acid salt or hydroxide of aluminum, organic salt or inorganic salt of calcium, iron, magnesium and lithium, a silicon-containing compound and an alcamines organic matter;
the liquid B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or a derivative thereof;
mixing the solution A and the solution B according to the mass ratio of 3-8: 1.
In the invention, 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 invention, 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 present invention, the alcohol amine includes at least one of polyalcohol amine, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, and diglycolamine.
In the invention, the small monomer comprises methacrylic acid and polyalcohol, and the polyalcohol comprises polyethylene glycol or polyglycerol.
In the present invention, the sulfonate or its derivative includes at least one of lignosulfonate and α -olefin sulfonate.
In the invention, the reducing agent comprises at least one of vitamin C, sodium formaldehyde sulfoxylate, ferric sulfite, sodium metabisulfite, sodium bisulfite, sodium hypophosphite and glucose,
the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
Secondly, the invention provides a preparation method of an alkali-free accelerator resisting the alkali activity reaction of aggregate, which comprises the following steps:
preparation of S1A solution
Adding water into a reaction kettle, adding aluminum acid salt or hydroxide, heating, continuously adding organic salt or inorganic salt of calcium, iron, magnesium and lithium and alcohol amine organic matter,
continuously stirring until the added substances are dissolved in the adding process, and cooling to normal temperature to obtain solution A;
preparation of S2B solution
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 a derivative thereof and the rest hypophosphite after the reaction is finished, stirring for reaction, and cooling to normal temperature to obtain a solution B;
blending the S3A liquid and the B liquid
And blending 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 invention, the liquid A and the liquid B are cooled to normal temperature and are mixed and reacted according to a proportion, so that the liquid AB is subjected to a crosslinking reaction, and the liquid AB is more uniform and stable compared with a conventional physical mixing system. In the invention, after the temperature is raised, a 4-dimethylaminopyridine aqueous solution with the mass fraction of 5% is dripped for 80min, and the addition amount of the 4-dimethylaminopyridine aqueous solution is 3-6%. And (3) carrying out the reaction of the AB liquid to enable hydroxyl in the B liquid and a compound in the A liquid to generate complexation to form a complex, wherein the formed complex can still show the properties of the original two compounds, the complex also has an inhibitory effect on active aggregate in a concrete material, the durability of the concrete is enhanced, and after the reaction is finished, cooling to the normal temperature to obtain the high-performance alkali-resistant active sprayed concrete accelerator.
In the present invention, the temperature in S1 was raised to 85 ℃ and the temperature in S2 was raised to 60 ℃.
< example >
Example 1
An alkali-free accelerator for resisting the alkali activity reaction of aggregate is prepared from the alkali-free accelerator,
350kg of water is added into the reaction kettle A, 350kg of aluminum sulfate is heated 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 the mixture is continuously stirred until the magnesium fluosilicate and the aluminum hydroxide are completely dissolved, and the stirring is carried out for about 0.5 hour. Continuously adding 50kg of magnesium sulfate, 60kg of lithium phosphate and 30kg of lithium ferrate into the reaction kettle A, stirring for about 0.5h, continuously adding 60kg of triethanolamine, stirring for reaction, and keeping the temperature for 20min after the solution is clarified. And after the heat preservation is finished, cooling to normal temperature to obtain 1.5 tons of product A liquid.
And adding 300kg of water, 300kg of acrylic acid, 100kg of methacrylic acid, 70kg of polyethylene glycol, 5kg of ammonium persulfate, 1kg of vitamin C and 10kg of lithium hypophosphite into the other reaction kettle B, 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 the normal temperature to obtain 1.0 ton of product B liquid.
And mixing and stirring the product A liquid and the product B liquid according to the mass ratio of 5:1, heating to 40-50 ℃, dropwise adding 100kg of 5% mass fraction 4-dimethylaminopyridine aqueous solution at a constant speed for 80min, after the reaction is finished, keeping the temperature for 20min, 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 is prepared from the alkali-free accelerator,
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 the mixture is continuously stirred until the mixture is completely dissolved for about 0.5 h. 120kg of magnesium sulfate and 20kg of lithium oxalate were continuously charged into the reaction vessel A, followed by stirring for about 0.5 hour. And continuously adding 60kg of polyalcohol amine, stirring for reaction, keeping the temperature of the solution uniform for 20min, and cooling to normal temperature to obtain 1.5 tons of product A liquid.
And adding 330kg of water, 270kg of acrylic acid, 100kg of methacrylic acid, 70kg of polyglycerol, 5kg of ammonium persulfate, 1kg of vitamin C and 10kg of ammonium hypophosphite into the other reaction kettle B, 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 the normal temperature to obtain 1.0 ton of a product B material.
And mixing and stirring the product A liquid and the product B liquid according to the mass ratio of 6:1, heating to 40-50 ℃, dropwise adding 100kg of 5% of 4-dimethylaminopyridine aqueous solution at constant speed for 80min, after the reaction is finished, keeping the temperature for 20min, and uniformly stirring to obtain the high-performance alkali-resistant active sprayed concrete accelerator.
Example 3
This example differs from example 1 in that the mass ratio of the solution a to the solution B was 3: 1.
Example 4
This example differs from example 1 in that the mass ratio of liquid a to liquid B was 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
This comparative example differs from example 1 in that no liquid B was added.
Comparative example 2
The comparative example is different from example 1 in that the mass ratio of the solution A to the solution B is 2: 1.
Comparative example 3
The comparative example is different from example 1 in that the mass ratio of the solution A to the solution B is 9: 1.
< test example >
The performance of the accelerating agent prepared in examples 1-5 and comparative examples 1-3 is measured, and the results show that the examples 1-5 all meet the relevant standards of the accelerating agent for the sprayed concrete GB/T35159 and 2017.
Standard tests were carried out on the above samples (example 1, examples 3 to 5, comparative examples 1 to 3), and the test results are shown in Table 1.
TABLE 1 test results
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The alkali-free accelerator for resisting the alkali activity reaction of the aggregate is characterized by comprising the following raw materials:
the liquid A comprises water, an acid salt or hydroxide of aluminum, organic salt or inorganic salt of calcium, iron, magnesium and lithium, a silicon-containing compound and an alcamines organic matter;
the liquid B comprises water, a mixture of acrylic acid and small monomers, a reducing agent, an initiator, hypophosphite and sulfonate or a derivative thereof;
mixing the solution A and the solution B according to the mass ratio of 3-8: 1.
2. The alkali-free accelerator agent for resisting the alkali activity reaction of aggregates according to claim 1, wherein 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.
3. The alkali-free accelerator agent for accelerating alkali-activated reactions of aggregates according to claim 1, wherein the organic or inorganic salts of calcium, iron, magnesium, lithium comprise at least one of magnesium sulfate, magnesium nitrate, calcium nitrate, lithium phosphate, and lithium ferrate.
4. The alkali-free accelerator agent for aggregate alkali activity reaction according to claim 1, wherein the alcohol amine comprises at least one of polyalcohol amine, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, diglycolamine.
5. The alkali-free accelerator agent for accelerating alkali-activated reaction of aggregate according to claim 1, wherein the small monomer comprises methacrylic acid and polyol, and the polyol comprises polyethylene glycol or polyglycerol.
6. The alkali-free accelerator agent for accelerating alkali-activated reaction of aggregate according to claim 1 or 5, wherein the sulfonate or its derivative comprises at least one of lignosulfonate and α -olefin sulfonate.
7. The alkali-free accelerator agent for resisting the alkali activity reaction of the aggregate according to claim 1, wherein the reducing agent comprises at least one of vitamin C, sodium formaldehyde sulfoxylate, ferric sulfite, sodium metabisulfite, sodium bisulfite, sodium hypophosphite and glucose, and the initiator comprises at least one of sodium persulfate, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
8. A method for preparing an alkali-free accelerator agent for resisting an alkali-active reaction of aggregates according to any one of claims 1 to 7, comprising the steps of:
preparation of S1A solution
Adding water into a reaction kettle, adding an aluminum acid salt or hydroxide, heating, continuously adding organic salt or inorganic salt of calcium, iron, magnesium and lithium, a silicon-containing compound and an alcohol amine organic matter,
continuously stirring until the added substances are dissolved in the adding process, and cooling to normal temperature to obtain solution A;
preparation of S2B solution
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 a derivative thereof and the rest hypophosphite after the reaction is finished, stirring for reaction, and cooling to normal temperature to obtain a solution B;
blending the S3A liquid and the B liquid
And blending the solution A and the solution B in proportion, heating to 40-50 ℃, and carrying out heat preservation treatment to obtain the accelerator.
9. The preparation method of the alkali-free accelerator capable of resisting the alkali activity reaction of the aggregate according to claim 8, wherein a 5% by mass aqueous solution of 4-dimethylaminopyridine is dropwise added after the temperature is raised, the dropwise addition time is 80min, and the addition amount of the aqueous solution of 4-dimethylaminopyridine is 3-6%.
10. The method for preparing an alkali-free accelerator agent for accelerating alkali-activated reaction of aggregate according to claim 8 or 9, wherein the temperature is raised to 85 ℃ in S1 and 60 ℃ in S2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116283145A (en) * | 2023-03-14 | 2023-06-23 | 西南交通大学 | High-strength and high-toughness heat-insulation functional sprayed concrete for high-temperature hot water tunnel |
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