CN115572099A - Normal-temperature preparation method of alkali-free liquid accelerator for quick-hardening early-strength sprayed concrete - Google Patents
Normal-temperature preparation method of alkali-free liquid accelerator for quick-hardening early-strength sprayed concrete Download PDFInfo
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- CN115572099A CN115572099A CN202211332694.XA CN202211332694A CN115572099A CN 115572099 A CN115572099 A CN 115572099A CN 202211332694 A CN202211332694 A CN 202211332694A CN 115572099 A CN115572099 A CN 115572099A
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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
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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
- C04B2103/12—Set 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
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Abstract
The invention discloses a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength shotcrete, which comprises the following steps: at normal temperature, water, aluminum sulfate, active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao are mixed and stirred to prepare the concrete accelerator. The concrete accelerator prepared by the invention has the advantages of short setting time, high early strength, no need of heating in the production process, capability of being carried out at normal temperature, greatly reduced production energy consumption and reduced process cost.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength shotcrete.
Background
The accelerator is a chemical admixture capable of quickly coagulating concrete and is widely applied to various tunnel projects. With the increasing level of spraying equipment, the liquid accelerator completely or partially replaces the powder accelerator and becomes a mainstream product used in the market at present. The high-alkalinity accelerating agent taking aluminate and silicate as main components is easy to corrode the skin of a human body due to strong alkalinity, and simultaneously, a series of durability problems such as later strength loss of concrete and the like are gradually eliminated. The low-alkali-free liquid accelerator is the main research direction at present, and has the advantages of quick setting time, high early strength and high later strength retention rate.
The existing alkali-free liquid accelerator is mainly of an aluminum sulfate system, and because the solubility of aluminum sulfate is limited, the doping amount of the alkali-free liquid accelerator is often large, and the doping amount of the alkali-free liquid accelerator even reaches 10 percent of the cement quality. The setting accelerator using hydrofluoric acid as a raw material has a very fast setting time, but a very low strength for 1 day. In the actual production process, in order to rapidly dissolve the aluminum sulfate, high-temperature heating is required to dissolve the aluminum sulfate, so that the production cost is increased. Therefore, the research on the alkali-free liquid accelerator which has quick setting time, high early strength and no need of heating production is very beneficial from the aspects of economy and environmental protection.
Disclosure of Invention
The invention mainly aims to provide a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength sprayed concrete, and aims to provide a concrete accelerator which is quick in setting time, high in early strength and free of heating in the production process.
In order to realize the aim, the invention provides a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength shotcrete, which comprises the following steps:
at normal temperature, water, aluminum sulfate, active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao are mixed and stirred to prepare the concrete accelerator.
Optionally, the step of preparing the active aluminate solution comprises:
adding sodium hydroxide into water, heating to 85-95 ℃, then adding aluminum hydroxide, keeping the temperature for reaction for 100-150 min after the addition is finished, and then adding phosphoric acid into the reaction product to obtain the active aluminate solution.
Optionally, the adding time of the aluminum hydroxide is controlled to be 50-70 min; and/or the presence of a gas in the gas,
the molar ratio of the sodium hydroxide to the aluminum hydroxide is 1.4-1.7; and/or the presence of a gas in the gas,
the adding amount of the phosphoric acid is 1-2.5% of the total mass of the water, the sodium hydroxide and the aluminum hydroxide.
Optionally, the modified aluminum hydroxide is prepared by the steps of:
preparing the aluminum hydroxide into the aluminum hydroxide with the specific surface area of 600-800 m 2 (kg) of powder, and then adding methacrylic acid dropwise into the powder to obtain modified aluminum hydroxide。
Optionally, the aluminum hydroxide is prepared to have a specific surface area of 600-800 m 2 A powder/kg step comprising:
and (3) placing the aluminum hydroxide in a ball mill, and grinding for 2-4 h to obtain powder.
Optionally, the amount of methacrylic acid added is 2 to 4% by mass of the aluminum hydroxide.
Optionally, the mass ratio of the aluminum sulfate, the lithium sulfate, the magnesium aluminum silicate, the superfine aluminum silicate, wen Lunjiao, the activated aluminate solution, the modified aluminum hydroxide, the fluosilicic acid, the diethanol amine, the triisopropanolamine and the sorbitol is 370-30.
Optionally, the step of mixing and stirring water, aluminum sulfate, an active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanolamine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao at normal temperature to prepare the concrete accelerator comprises the following steps:
adding superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao into water at normal temperature, and stirring for the first time to obtain a first solution;
adding aluminum sulfate, an active aluminate solution and modified aluminum hydroxide into the first solution in sequence, and stirring for the second time to obtain a second solution;
dropwise adding fluosilicic acid into the second solution, stirring for the third time, adding diethanolamine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for the fourth time to obtain a third solution;
and adding lithium sulfate into the third solution, and stirring for the fifth time to obtain the concrete accelerator.
Optionally, the stirring speed of the first stirring is 600-800 rpm, and the stirring time is 20-40 min; and/or the presence of a gas in the gas,
the stirring speed of the second stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the presence of a gas in the atmosphere,
the stirring speed of the third stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the presence of a gas in the gas,
the stirring speed of the fourth stirring is 200-300 rpm, and the stirring time is 15-25 min; and/or the presence of a gas in the gas,
the stirring speed of the fifth stirring is 600-800 rpm, and the stirring time is 1.5-2.5 h.
Optionally, the fluorosilicic acid has a solubility of 35 to 40%.
In the technical scheme provided by the invention, the raw materials for preparing the concrete accelerator comprise aluminum sulfate, an active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao, wherein the aluminum sulfate, the active aluminate solution and the modified aluminum hydroxide are used as coagulation accelerating components for improving the content of aluminum ions in cement, generating ettringite and improving the coagulation accelerating effect; the diethanol amine, the triethanolamine, the sorbitol, the fluosilicic acid, the Wen Lun glue and the superfine aluminum silicate are used as stable components, the fluosilicic acid, the diethanol amine and the triethanolamine are used as aluminum ion complexing agents, and three suspending agents are compounded to improve the stability of the accelerator; lithium sulfate is used as a reinforcing component, and the strength of the cement is improved by introducing lithium ions; the concrete accelerator prepared by the method has the advantages of short setting time and high early strength, and can be carried out at normal temperature without heating in the production process, so that the production energy consumption is greatly reduced, and the process cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of an embodiment of a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength shotcrete provided by the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of 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. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a normal-temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength sprayed concrete, and on the first hand, aiming at the phenomenon that the solubility of aluminum sulfate is not high and the phenomenon that the aluminum sulfate is unstable easily in a supersaturated state of the solubility, the invention adopts fluosilicic acid as an aluminum ion complexing agent to realize that the accelerator has a better accelerating effect under a lower doping amount. In the second aspect, the introduction of fluoride ions can realize the rapid setting and hardening of cement, but insoluble calcium fluoride is generated with the cement and wraps the surface of unhydrated cement clinker, so that the early strength of the cement is relatively low, and therefore, the early strength of the concrete is ensured by introducing an active aluminate solution and alcohol amine; meanwhile, several high-efficiency suspending agents are compounded, so that the stability of the accelerator is improved under the condition of high-speed dispersion. In the third aspect, the content of aluminum sulfate in the alkali-free liquid accelerator of an aluminum sulfate system is usually more than 50%, and aluminum sulfate is difficult to dissolve at normal temperature, so that the aluminum sulfate is automatically dissolved at a certain temperature by adopting an acid-base neutralization exothermic reaction without additional heating, thereby achieving the purpose of energy conservation.
Specifically, in some embodiments of the present invention, the method for preparing the alkali-free liquid accelerator for quick-hardening early strength shotcrete at normal temperature comprises the following steps: at normal temperature, water, aluminum sulfate, active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao are mixed and stirred to prepare the concrete accelerator.
In the technical scheme provided by the invention, the preparation raw materials of the concrete accelerator comprise aluminum sulfate, active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao, wherein the aluminum sulfate, the active aluminate solution and the modified aluminum hydroxide are used as accelerating components for increasing the content of active aluminum ions in the accelerator, generating ettringite and improving the accelerating effect on cement; the stabilizing component is diethanol amine, triethanolamine, sorbitol, fluosilicic acid, wen Lun glue and superfine aluminum silicate, the fluosilicic acid, the diethanol amine, the triethanolamine and the sorbitol are used as aluminum ion complexing agents, and three suspending agents of the superfine aluminum silicate, the magnesium aluminum silicate and Wen Lunjiao are compounded to improve the stability of the accelerator, so that the accelerator does not have the phenomenon of precipitation and delamination; the lithium sulfate is used as a reinforcing component, and the early strength of the cement is improved by introducing lithium ions, so that favorable support is provided for the secondary lining. The concrete accelerator prepared by the method has the advantages of short setting time and high early strength, and can be carried out at normal temperature without heating in the production process, so that the production energy consumption is greatly reduced, and the process cost is reduced.
The active aluminate solution and the modified aluminum hydroxide have the effects of increasing the content of active aluminum ions in the accelerator, and simultaneously, when reacting with fluosilicic acid, the temperature can be spontaneously raised, so that consumption reduction and energy conservation are realized. In some embodiments of the present invention, the method for preparing the alkali-free liquid accelerator for quick-hardening early strength shotcrete at an ordinary temperature further comprises the step of preparing the active aluminate solution by itself. Specifically, the preparation steps of the active aluminate solution comprise: adding sodium hydroxide into water, heating to 85-95 ℃, then adding aluminum hydroxide, keeping the temperature for reaction for 100-150 min after the addition is finished, and then adding phosphoric acid into the reaction product to obtain the active aluminate solution.
Firstly, pouring a certain amount of water into a reaction vessel with a mechanical stirring device, then adding sodium hydroxide into the reaction vessel, releasing heat in the reaction, slowly adding aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 50-70 min, after the adding is finished, keeping the temperature and reacting for 100-150 min, and then adding a certain amount of phosphoric acid into the obtained reaction product to obtain the active aluminate solution.
Further, in some embodiments of the invention, the molar ratio of the sodium hydroxide to the aluminum hydroxide is 1.4 to 1.7.
In some embodiments of the present invention, the amount of phosphoric acid added is 1 to 2.5% of the total mass of the water, sodium hydroxide and aluminum hydroxide.
In some embodiments of the invention, the normal-temperature preparation method of the alkali-free liquid accelerator for quick-hardening early-strength shotcrete further comprises the step of preparing the modified aluminum hydroxide by self. Specifically, the preparation steps of the modified aluminum hydroxide comprise: preparing the aluminum hydroxide into the aluminum hydroxide with the specific surface area of 600-800 m 2 And (2) adding methacrylic acid dropwise into the powder material to obtain the modified aluminum hydroxide.
Further, in some embodiments of the present invention, the aluminum hydroxide is prepared to have a specific surface area of 600 to 800m 2 The steps of the powder material per kg comprise: and (3) placing the aluminum hydroxide in a ball mill, and grinding for 2-4 h to obtain powder.
In some embodiments of the present invention, the methacrylic acid is added in an amount of 2 to 4% by mass of the aluminum hydroxide.
The invention screens out the optimal material and the mixing proportion thereof by researching, collecting and detecting the raw materials, wherein, in some embodiments of the invention, the preferred solubility of the fluosilicic acid is 35-40%. Further, the mixing ratio of the materials is as follows: the mass ratio of the aluminum sulfate, the lithium sulfate, the magnesium aluminum silicate, the superfine aluminum silicate, the Wen Lunjiao, the activated aluminate solution, the modified aluminum hydroxide, the fluosilicic acid, the diethanol amine, the triisopropanolamine and the sorbitol is 370-12-6:4-6. The concrete accelerator prepared by the mixing proportion has the advantages that the setting time and the compressive strength meet the standard requirements, the concrete accelerator can be stored for a long time without precipitation, the alkali ion content is low, and the environment is not polluted.
In an embodiment of the present invention, referring to fig. 1, a method for preparing an alkali-free liquid accelerator for quick-hardening early-strength shotcrete at normal temperature specifically includes the following steps:
step S10, adding superfine aluminum silicate, aluminum magnesium silicate and Wen Lunjiao into water at normal temperature, and stirring for the first time to obtain a first solution;
s20, sequentially adding aluminum sulfate, an active aluminate solution and modified aluminum hydroxide into the first solution, and stirring for the second time to obtain a second solution;
step S30, dripping fluosilicic acid into the second solution, carrying out third stirring, adding diethanolamine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and carrying out fourth stirring to obtain a third solution;
and S40, adding lithium sulfate into the third solution, and stirring for the fifth time to obtain the concrete accelerator.
In this example, the water used was distilled water and the materials used were all of analytical grade. Firstly, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding three suspending agents of superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao into the water, uniformly mixing, and then stirring for the first time; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for the second time; then, dripping fluosilicic acid, stirring for the third time, automatically heating a reaction system in the process, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for the fourth time; and finally adding lithium sulfate, and stirring for the fifth time to obtain the concrete accelerator at normal temperature.
Specifically, the stirring speed of the first stirring is 600-800 rpm, and the stirring time is 20-40 min; and/or the stirring speed of the second stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the stirring speed of the third stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the stirring speed of the fourth stirring is 200-300 rpm, and the stirring time is 15-25 min; and/or the stirring speed of the fifth stirring is 600-800 rpm, and the stirring time is 1.5-2.5 h. The stirring rotation speeds of the first stirring and the fifth stirring may be the same or different from each other, and similarly, the stirring rotation speeds of the second stirring, the third stirring, and the fourth stirring may be the same or different from each other, and all of them fall within the scope of the present invention.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 50min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.4.
(2) The aluminum hydroxide is put into a ball mill for grinding for 2 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the addition amount of the methacrylic acid is 2 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 370 parts of aluminum sulfate, 25 parts of lithium sulfate, 12 parts of magnesium aluminum silicate, 4 parts of superfine aluminum silicate, 4 parts of Wen Lun glue, 45 parts of active aluminate solution, 85 parts of modified aluminum hydroxide, 145 parts of fluosilicic acid, 35 parts of diethanolamine, 6 parts of triisopropanolamine and 6 parts of sorbitol according to the parts by weight;
at normal temperature, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding the weighed three suspending agents of superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao into the water, uniformly mixing, and then stirring at a high speed of 600rpm for 40min; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for 70min at the rotating speed of 200 rpm; then, dropwise adding fluosilicic acid, stirring for 70min at the rotating speed of 200rpm, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for 25min at the rotating speed of 200 rpm; and finally adding lithium sulfate, and stirring at the rotating speed of 600rpm for 2.5 hours to obtain the concrete accelerator at normal temperature.
Example 2
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.5.
(2) The aluminum hydroxide is put into a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the addition amount of the methacrylic acid is 2.5 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 370 parts of aluminum sulfate, 28 parts of lithium sulfate, 13 parts of magnesium aluminum silicate, 5 parts of superfine aluminum silicate, 5 parts of Wen Lun glue, 47 parts of active aluminate solution, 88 parts of modified aluminum hydroxide, 146 parts of fluosilicic acid, 37 parts of diethanolamine, 9 parts of triisopropanolamine and 9 parts of sorbitol according to the parts by weight;
at normal temperature, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding the weighed superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao three suspending agents into the water, uniformly mixing, and stirring at a high speed of 700rpm for 30min; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for 60min at the rotating speed of 250 rpm; then, dripping fluosilicic acid, stirring for 60min at the rotating speed of 250rpm, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for 20min at the rotating speed of 250 rpm; and finally adding lithium sulfate, and stirring at the rotating speed of 700rpm for 2 hours to obtain the concrete accelerator at normal temperature.
Example 3
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 70min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.7.
(2) The aluminum hydroxide is put into a ball mill and ground for 4 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the adding amount of the methacrylic acid is 3 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 370 parts of aluminum sulfate, 30 parts of lithium sulfate, 15 parts of magnesium aluminum silicate, 6 parts of superfine aluminum silicate, 6 parts of Wen Lun glue, 50 parts of active aluminate solution, 90 parts of modified aluminum hydroxide, 150 parts of fluosilicic acid, 40 parts of diethanolamine, 10 parts of triisopropanolamine and 10 parts of sorbitol according to the parts by weight;
at normal temperature, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding the weighed three suspending agents of ultrafine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao into the water, uniformly mixing, and then stirring at a high speed of 800rpm for 20min; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for 50min at the rotating speed of 300 rpm; then, dropwise adding fluosilicic acid, stirring for 50min at the rotating speed of 300rpm, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for 15min at the rotating speed of 300 rpm; and finally adding lithium sulfate, and stirring at the rotating speed of 800rpm for 1.5h to obtain the concrete accelerator at normal temperature.
Example 4
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding the aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.6.
(2) The aluminum hydroxide is put into a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the addition amount of the methacrylic acid is 3.5 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 370 parts of aluminum sulfate, 25 parts of lithium sulfate, 15 parts of magnesium aluminum silicate, 6 parts of superfine aluminum silicate, 6 parts of Wen Lun glue, 45 parts of active aluminate solution, 85 parts of modified aluminum hydroxide, 150 parts of fluosilicic acid, 35 parts of diethanolamine, 10 parts of triisopropanolamine and 10 parts of sorbitol according to the parts by weight;
at normal temperature, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding the weighed superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao three suspending agents into the water, uniformly mixing, and stirring at a high speed of 700rpm for 30min; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for 60min at the rotating speed of 250 rpm; then, dropwise adding fluosilicic acid, stirring for 60min at the rotating speed of 250rpm, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for 20min at the rotating speed of 250 rpm; and finally adding lithium sulfate, and stirring at the rotating speed of 700rpm for 2 hours to obtain the concrete accelerator at normal temperature.
Example 5
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.5.
(2) The aluminum hydroxide is put into a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 And (2) adding methacrylic acid (the adding amount of the methacrylic acid is 4 percent of the mass of the aluminum hydroxide) dropwise into the powder to obtain the modified aluminum hydroxide.
(3) Weighing 370 parts of aluminum sulfate, 30 parts of lithium sulfate, 14 parts of magnesium aluminum silicate, 5 parts of superfine aluminum silicate, 4 parts of Wen Lun glue, 48 parts of active aluminate solution, 90 parts of modified aluminum hydroxide, 147 parts of fluosilicic acid, 40 parts of diethanolamine, 6 parts of triisopropanolamine and 7 parts of sorbitol according to the parts by weight;
at normal temperature, adding a certain mass of water into a reaction container provided with a mechanical stirring device, adding the weighed superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao three suspending agents into the water, uniformly mixing, and stirring at a high speed of 700rpm for 30min; then sequentially adding an active aluminate solution and modified aluminum hydroxide, and stirring for 60min at the rotating speed of 250 rpm; then, dripping fluosilicic acid, stirring for 60min at the rotating speed of 250rpm, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for 20min at the rotating speed of 250 rpm; and finally adding lithium sulfate, and stirring at the rotating speed of 700rpm for 2 hours to obtain the concrete accelerator at normal temperature.
Comparative example 1
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding the aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.5.
(2) Aluminum hydroxide is placed in a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the adding amount of the methacrylic acid is 3 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 280 parts of water, 20 parts of superfine aluminum silicate, 50 parts of active aluminate solution, 90 parts of modified aluminum hydroxide, 360 parts of aluminum sulfate, 30 parts of magnesium sulfate, 150 parts of fluosilicic acid, 10 parts of triethanolamine and 10 parts of sorbitol;
at normal temperature, adding weighed water into a reaction container provided with a mechanical stirring device, firstly adding superfine aluminum silicate, stirring at a high speed of 700rpm for 30min, then sequentially adding an active aluminate solution and modified aluminum hydroxide, stirring at a speed of 250rpm for 1h, then dropwise adding fluosilicic acid, stirring at a speed of 250rpm for 1h, adding triethanolamine and sorbitol when the temperature of the materials rises to 60-70 ℃, stirring at a speed of 250rpm for 20min, finally adding magnesium sulfate, and stirring at a speed of 700rpm for 2h to prepare the concrete accelerator.
Comparative example 2
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding the aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.5.
(2) The aluminum hydroxide is put into a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 The modified aluminum hydroxide is obtained by adding methacrylic acid (the adding amount of the methacrylic acid is 3 percent of the mass of the aluminum hydroxide) dropwise into the powder.
(3) Weighing 250 parts of water, 12 parts of magnesium aluminum silicate, 4 parts of superfine aluminum silicate, 4 parts of Wen Lun glue, 50 parts of active aluminate solution, 90 parts of modified aluminum hydroxide, 390 parts of aluminum sulfate, 30 parts of magnesium sulfate, 150 parts of fluosilicic acid, 10 parts of triethanolamine and 10 parts of sorbitol;
at normal temperature, adding weighed water into a reaction container provided with a mechanical stirring device, firstly adding superfine aluminum silicate, wen Lun glue and magnesium aluminum silicate, stirring at a high speed of 700rpm for 30min, then sequentially adding an active aluminate solution and modified aluminum hydroxide, stirring at a speed of 250rpm for 1h, then dropwise adding fluosilicic acid, stirring at a speed of 250rpm for 1h, adding triethanolamine and sorbitol when the temperature of the materials rises to 60-70 ℃, stirring at a speed of 250rpm for 20min, finally adding magnesium sulfate, and stirring at a speed of 700rpm for 2h to prepare the concrete accelerator.
Comparative example 3
(1) Pouring water with the mass 1.5 times that of sodium hydroxide into a reaction vessel with a mechanical stirring device, then adding the sodium hydroxide into the reaction vessel, carrying out reaction heat release, slowly adding the aluminum hydroxide into the reaction vessel when the temperature is raised to 85-95 ℃, controlling the adding time of the aluminum hydroxide to be 60min, controlling the molar ratio of the sodium hydroxide to the aluminum hydroxide to be 1.5.
(2) Aluminum hydroxide is placed in a ball mill and ground for 3 hours to prepare the aluminum hydroxide with the specific surface area of 600-800 m 2 /kg of powder, and then adding methacrylic acid (the addition amount of the methacrylic acid is 3 percent of the mass of the aluminum hydroxide) dropwise into the powder to obtain the modified aluminum hydroxide.
(3) Weighing 230 parts of water, 12 parts of magnesium aluminum silicate, 4 parts of superfine aluminum silicate, 4 parts of Wen Lun glue, 50 parts of active aluminate solution, 90 parts of modified aluminum hydroxide, 370 parts of aluminum sulfate, 30 parts of magnesium sulfate, 150 parts of fluosilicic acid, 40 parts of diethanolamine, 10 parts of triethanolamine and 10 parts of sorbitol;
at normal temperature, adding weighed water into a reaction container provided with a mechanical stirring device, firstly adding superfine aluminum silicate, wen Lun glue and magnesium aluminum silicate, stirring at a high speed of 700rpm for 30min, then sequentially adding an active aluminate solution and modified aluminum hydroxide, stirring at a speed of 250rpm for 1h, then dropwise adding fluosilicic acid, stirring at a speed of 250rpm for 1h, adding diethanol amine, triethanolamine and sorbitol when the temperature of the materials rises to 60-70 ℃, stirring at a speed of 250rpm for 20min, finally adding magnesium sulfate, and stirring at a speed of 700rpm for 2h to prepare the concrete accelerator.
The concrete accelerators obtained in the above examples 1 to 8 and comparative examples 1 to 3 were tested for quick setting performance and compressive strength, respectively, and the test methods and test results were as follows:
the test method comprises the following steps: preparing a cement paste sample by using an NJ-160 type cement paste stirrer for an experimental sample; measuring the initial setting time and the final setting time of the material by using a cement consistency setting time measuring instrument; preparing a mortar sample with the size of 40mm multiplied by 160mm by adopting a JJ-5 type mortar stirrer and a ZS-15 type mortar vibrating table, and putting the mortar sample into a YH-40B cement constant-temperature constant-humidity standard curing box for curing; the compressive strength of the material is measured by utilizing a DYW-300S type computer full-automatic cement bending and compression resistant integrated machine. The measurement is carried out according to the GB/T35159-2017 accelerator for sprayed concrete.
The test results of examples 1 to 8 and comparative examples 1 to 3 are shown in table 1 below.
TABLE 1 test results of quick setting property and compressive strength of examples and comparative examples
As can be seen from the test results in Table 1, the concrete accelerator prepared according to the formulation adopted in comparative example 1 has too slow setting time, precipitation and delamination occurred in 3 days of stability, and the compressive strength did not reach the standard. Comparative example 2 tries to increase the use amount of aluminum sulfate to improve the setting time, the stability is improved by compounding three suspending agents of superfine aluminum silicate, aluminum magnesium silicate and Wen Lunjiao, the setting time of the prepared concrete accelerator meets the standard requirement, but layered precipitation appears in 15 days of stability, and the compressive strength does not meet the standard requirement. Comparative example 3 attempts to increase the stability of the accelerator by adding diethanolamine, and the setting time and compressive strength of the prepared concrete accelerator meet the standard requirements, but the compressive strength needs to be further increased. According to the embodiment of the invention, lithium sulfate is adopted to replace magnesium sulfate, so that the setting time and the compressive strength of the prepared concrete accelerator both meet the standard requirements, the compressive strength is obviously improved, and the concrete accelerator can be stored for a long time without precipitation, has low alkali ion content and causes no pollution to the environment.
In order to further confirm the performance of the concrete accelerator prepared in the examples of the present invention, the performance of the accelerator was tested, and the results of the tests are shown in table 2 below.
TABLE 2 main technical and economic indexes of concrete accelerator prepared in example and comparative analysis at home and abroad
The test results in the table 2 show that the concrete accelerator prepared by the embodiment of the invention completely meets the requirements of relevant technical specifications, has no damage to the strength of concrete, has various functional indexes and quality far superior to similar products in the market, and has wide market application and development prospects.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A normal temperature preparation method of an alkali-free liquid accelerator for quick-hardening early-strength shotcrete is characterized by comprising the following steps:
at normal temperature, water, aluminum sulfate, active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanol amine, triisopropanolamine, sorbitol, superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao are mixed and stirred to prepare the concrete accelerator.
2. The method for preparing the alkali-free liquid accelerator for quick-hardening early-strength shotcrete according to claim 1, wherein the step of preparing the active aluminate solution comprises:
adding sodium hydroxide into water, heating to 85-95 ℃, then adding aluminum hydroxide, keeping the temperature for reaction for 100-150 min after the addition is finished, and then adding phosphoric acid into the reaction product to obtain the active aluminate solution.
3. The normal-temperature preparation method of the alkali-free liquid accelerator for the quick-hardening early-strength shotcrete as claimed in claim 2, wherein the adding time of the aluminum hydroxide is controlled to be 50-70 min; and/or the presence of a gas in the atmosphere,
the molar ratio of the sodium hydroxide to the aluminum hydroxide is 1.4-1.7; and/or the presence of a gas in the atmosphere,
the adding amount of the phosphoric acid is 1-2.5% of the total mass of the water, the sodium hydroxide and the aluminum hydroxide.
4. The method for preparing the alkali-free liquid accelerator for quick-hardening early-strength shotcrete according to claim 1, wherein the modified aluminum hydroxide is prepared by the steps of:
preparing the aluminum hydroxide into the aluminum hydroxide with the specific surface area of 600-800 m 2 And (2) adding methacrylic acid dropwise into the powder material to obtain the modified aluminum hydroxide.
5. The method for preparing the alkali-free liquid accelerator for quick-hardening early-strength shotcrete as claimed in claim 4, wherein the aluminum hydroxide is prepared to have a specific surface area of 600-800 m 2 A powder/kg step comprising:
and (3) placing the aluminum hydroxide in a ball mill, and grinding for 2-4 h to obtain powder.
6. The method for preparing the alkali-free liquid accelerator for quick-hardening early-strength shotcrete as claimed in claim 4, wherein the amount of the methacrylic acid added is 2-4% by mass of the aluminum hydroxide.
7. The normal temperature preparation method of the alkali-free liquid accelerator for the quick-hardening early-strength shotcrete as claimed in claim 1, wherein the mass ratio of the aluminum sulfate, the lithium sulfate, the magnesium aluminum silicate, the superfine aluminum silicate, the Wen Lunjiao, the activated aluminate solution, the modified aluminum hydroxide, the fluosilicic acid, the diethanolamine, the triisopropanolamine and the sorbitol is 370-30.
8. The method for preparing the alkali-free accelerator for quick-hardening early-strength shotcrete as claimed in claim 1, wherein the step of mixing and stirring water, aluminum sulfate, an active aluminate solution, modified aluminum hydroxide, fluosilicic acid, lithium sulfate, diethanolamine, triisopropanolamine, sorbitol, ultra-fine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao at normal temperature to prepare the concrete accelerator comprises:
adding superfine aluminum silicate, magnesium aluminum silicate and Wen Lunjiao into water at normal temperature, and stirring for the first time to obtain a first solution;
adding aluminum sulfate, an active aluminate solution and modified aluminum hydroxide into the first solution in sequence, and stirring for the second time to obtain a second solution;
dropwise adding fluosilicic acid into the second solution, stirring for the third time, adding diethanolamine, triethanolamine and sorbitol when the temperature of the materials reaches 60-70 ℃, and stirring for the fourth time to obtain a third solution;
and adding lithium sulfate into the third solution, and stirring for the fifth time to obtain the concrete accelerator.
9. The normal-temperature preparation method of the alkali-free liquid accelerator for quick-hardening early-strength shotcrete as claimed in claim 8, wherein the stirring speed of the first stirring is 600-800 rpm, and the stirring time is 20-40 min; and/or the presence of a gas in the gas,
the stirring speed of the second stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the presence of a gas in the gas,
the stirring speed of the third stirring is 200-300 rpm, and the stirring time is 50-70 min; and/or the presence of a gas in the gas,
the stirring speed of the fourth stirring is 200-300 rpm, and the stirring time is 15-25 min; and/or the presence of a gas in the gas,
the stirring speed of the fifth stirring is 600-800 rpm, and the stirring time is 1.5-2.5 h.
10. The method for preparing the alkali-free liquid accelerator for quick-hardening early-strength shotcrete as claimed in claim 1, wherein the solubility of the fluorosilicic acid is 35-40%.
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