CN110627397B - High-strength alkali-free liquid accelerator, preparation method and application thereof - Google Patents
High-strength alkali-free liquid accelerator, preparation method and application thereof Download PDFInfo
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- CN110627397B CN110627397B CN201910802635.6A CN201910802635A CN110627397B CN 110627397 B CN110627397 B CN 110627397B CN 201910802635 A CN201910802635 A CN 201910802635A CN 110627397 B CN110627397 B CN 110627397B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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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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Abstract
The invention discloses a high-strength alkali-free liquid accelerator which comprises the following components in parts by weight: 30-50 parts of aluminum sulfate; 3-8 parts of aluminum hydroxide; 5-25 parts of hydrofluoric acid; 0-20 parts of magnesium sulfate; 1.0-3.0 parts of magnesium oxide; 0.5-3 parts of fluorosilicate; 0.3-1.2 parts of an emulsifier; 0.2-1.0 part of a stabilizer; 30-50 parts of water. The preparation method of the high-strength alkali-free liquid accelerator comprises the following steps of S1: preparing a fluorine-aluminum complex solution, weighing the following materials in proportion, firstly adding water, a stabilizer, fluosilicate and aluminum hydroxide, adding a hydrofluoric acid solution after pre-dispersion, obtaining a mixed solution after reaction is finished, and preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated; s2: preparing an alkali-free accelerator; and after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and an emulsifier according to a proportion, putting the materials into the mixed solution, adding magnesium oxide after reacting for a certain time, continuing to react, and obtaining the high-strength alkali-free accelerator after the reaction is finished.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a high-strength alkali-free liquid accelerator, a preparation method and application thereof.
Background
The liquid accelerator is an additive capable of quickly setting and hardening cement or concrete, is mainly used for wet-process sprayed concrete, and is widely applied to engineering projects such as high-speed rails, high-speed tunnels and subway tunnels.
The liquid accelerator comprises alkali, low-alkali and alkali-free liquid accelerators, and the alkali accelerator has the main problems of high alkali content, large 28d strength loss and strong corrosivity; the alkali-free (low-alkali) accelerator mainly has the problems of large mixing amount, short stabilization period and low 1d strength. In addition, because of the large cement output and the large number of production enterprises in China and the large difference of the mineral components and the types of mixed materials of the cement in different production areas, the compatibility problem of the cement and the accelerator often troubles technical personnel in the industry.
European patent US8075688B 2-Aqueous accelerater mixture using aluminum sulfate, active Al (OH)3The high early strength alkali-free accelerator is prepared from low-doping hydrofluoric acid, a stabilizer and the like, and has good adaptability; furthermore, European patent US8246742B2, Accelerator mix and method of use utilizes aluminum sulfate, active Al (OH)3Hydrofluoric acid orThe high early strength alkali-free setting accelerator prepared from fluosilicic acid, a stabilizer and the like has the compressive strength of 2MPa in 6 hours and 20MPa in 1 d.
Active Al (OH) used in the above two preparations3The raw materials are high in price and not easy to obtain, and industrial amorphous Al (OH) is difficult to purchase in China3Raw materials.
In addition, the invention patent 200910028321.1 discloses a liquid accelerator for sprayed concrete and its preparation method, which discloses an alkali-free accelerator containing aluminum sulfate, metal fluoride and amine as main components, and adding pH regulator and thickening substance, and its application range to cement is narrow and its mixing amount is large.
In conclusion, the existing accelerator has the technical problems of large mixing amount, narrow application range and high cost.
Disclosure of Invention
The invention provides a preparation method of a high-strength alkali-free liquid accelerator, which is used for solving the problems in the prior art that: the alkali-free liquid accelerator has the technical problems of narrow adaptability to cement, high mixing amount and high cost.
The invention aims to provide a high-strength alkali-free liquid accelerator which comprises the following components in parts by weight:
aluminum sulfate: 30-50 parts of aluminum hydroxide, 3-8 parts of hydrofluoric acid, 5-25 parts of magnesium sulfate, 1.0-3.0 parts of magnesium oxide, 0.5-3 parts of fluosilicate, 0.3-1.2 parts of emulsifier, 0.2-1.0 part of stabilizer and 30-50 parts of water.
In order to better realize the invention, further, 35-45 parts of aluminum sulfate, 4-6 parts of aluminum hydroxide, 12-16 parts of hydrofluoric acid, 5-15 parts of magnesium sulfate, 1.5-2.5 parts of magnesium oxide, 0.5-2 parts of fluosilicate, 0.4-0.8 part of emulsifier, 0.5-0.7 part of stabilizer and 35-45 parts of water.
In order to better realize the invention, the aluminum sulfate is 37 parts, the aluminum hydroxide is 7 parts, the hydrofluoric acid is 16 parts, the magnesium sulfate is 8 parts, the magnesium oxide is 2.4 parts, the fluosilicate is 1 part, the emulsifier is 0.8 part, the stabilizer is 0.7 part, and the water is 30 parts.
Further, the fluosilicate is magnesium fluosilicate or aluminum fluosilicate.
Further, magnesium fluorosilicate is preferable.
Further, the emulsifier is Tween-20, OP-10 or NP-4.
Further, Tween-20 is preferable.
Further, the stabilizing agent is precipitated hydrated magnesium silicate or attapulgite.
Further, precipitated hydrated magnesium silicate is preferable, and the precipitated hydrated magnesium silicate can disperse in a nano-scale state, so that the rheological property of a system can be improved, and the prepared accelerator has better stability.
Further, the aluminum sulfate, the magnesium sulfate, the stabilizer, the magnesium oxide, the aluminum hydroxide and the hydrofluoric acid are all industrial grade; the aluminum sulfate is Al2O3Industrial grade aluminum sulfate with content more than or equal to 16 percent.
Further, the hydrofluoric acid is an industrial hydrofluoric acid aqueous solution with the content of more than or equal to 30%.
The second purpose of the invention is to provide a preparation method of a high-strength alkali-free liquid accelerator, which comprises the following steps:
s1: preparation of the Fluoroaluminum Complex solution
Weighing the following materials in proportion, adding water, a stabilizer, fluorosilicate and aluminum hydroxide, pre-dispersing, adding a hydrofluoric acid solution, obtaining a mixed solution after the reaction is finished, and preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated;
s2: preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and an emulsifier according to a proportion, putting the materials into the mixed solution, adding magnesium oxide after reacting for a certain time, continuing to react, and obtaining the high-strength alkali-free accelerator after the reaction is finished.
In order to better realize the method, in the step S1, in preparing the fluorine-aluminum complex solution, the following materials are weighed according to a proportion, water, a stabilizer, fluorosilicate and aluminum hydroxide are added, after pre-dispersion is carried out for 0.5h, a hydrofluoric acid solution is continuously and slowly added, the reaction temperature is 90-95 ℃, a mixed solution is obtained after the reaction is finished, the mixed solution is subjected to heat preservation, and the heat preservation temperature is 85-90 ℃ until free hydrofluoric acid in the surplus mixed solution is fractionated.
In order to better realize the invention, the alkali-free accelerator is prepared in step S2, after fractionation is completed, heat preservation is stopped, the following materials, aluminum sulfate, magnesium sulfate and an emulsifier are weighed in proportion and put into the mixed solution, the reaction temperature is 60-65 ℃, magnesium oxide is added after stirring for 30min, after water is supplemented, stirring is continued for 1h, and after the reaction is completed, the temperature is reduced to room temperature to obtain the high-strength alkali-free accelerator.
The prior art for preparing alkali-free liquid setting accelerator is characterized in that F in the setting accelerator-Although the alkali-free setting accelerator has the function of quick setting, the depolymerization of hydrated product C-S-H gel of silicate mineral is easily caused, the polymerization degree of hydrated calcium silicate is reduced, the network structure of cement paste is damaged, the development of cement strength is seriously influenced, and the performance of the alkali-free setting accelerator is poorer.
The formula and the preparation method are adopted to prepare the high-strength alkali-free liquid accelerator, and after water, a stabilizer, fluorosilicate and aluminum hydroxide are reacted in the process of preparing the fluorine-aluminum complex solution, excessive hydrofluoric acid remained in the mixed solution is removed in a fractionation mode, so that the aim of improving the 1d strength of the accelerator is effectively guaranteed.
On the other hand, F-Ultra-strong complex Al3+Thereby increasing Al in the solution3+Or the concentration of free aluminum, can effectively ensure that the accelerator achieves the accelerating effect under the condition of low doping amount. Magnesium sulfate, magnesium oxide and magnesium fluosilicate provide magnesium ions to improve the adaptability of the accelerator to cement and improve early strength; the fluosilicate can be introduced into silicon, so that the early strength is improved; the magnesium oxide can be mixed with the pH value of the adjusting system to make the magnesium oxide in weak acidity, so that corrosion to construction tools and physical damage to constructors are avoided.
The alkali-free setting accelerator prepared by the formula and the preparation method has the advantages of high stability, low mixing amount, good practicability of cement, high early strength and 28d compressive strength ratio of more than 100%.
The preparation method is characterized in that the accelerator is prepared in a polytetrafluoroethylene reaction kettle, steam is used for heating through a coil pipe in the reaction kettle in a heating mode, and a spraying recovery device is used for treating volatile gas.
When the prepared low-doping-amount high-performance alkali-free liquid accelerator is used, a wet spraying process is adopted, cement cementing materials are added at a nozzle to prepare the shotcrete, and the doping amount is 4-6 wt%.
The third object of the present invention is to provide a high-strength alkali-free liquid accelerator.
The density of the alkali-free liquid accelerator is 1.3-1.5 g/cm3The pH value is 2.5-3.5, the solid content is 37-45%, and the alkali content is less than or equal to 1.0%.
The fourth purpose of the invention is to provide the application of the high-strength alkali-free liquid accelerator in the sprayed concrete.
The embodiment of the invention has the beneficial effects that:
the alkali-free liquid accelerator prepared by the method has strong adaptability and wide application range in the practical application process, is low in doping amount, and can improve the strength of 1d and the 28d compressive strength ratio is more than 100 percent;
in the preparation process of the invention, the invention uses F-Ultra-strong complex Al3+Thereby increasing Al in the solution3+Or the concentration of free aluminum, and simultaneously the precipitated hydrated magnesium silicate, the emulsifying agent and the stabilizing agent are used, the stability of the prepared liquid alkali-free accelerator is more than or equal to 6 months, the viscosity is low, and the liquid alkali-free accelerator is beneficial to on-site mechanical pumping construction;
the alkali-free liquid accelerator disclosed by the invention does not adopt expensive alcamines, the adopted formula is easy to obtain and low in cost, and the alkali-free liquid accelerator prepared by the synergistic action of the components in the formula disclosed by the invention has the advantages that the mixing amount of the accelerator prepared by the formula disclosed by the invention is small, the early strength is high, and the 28d compressive strength ratio is more than 100%;
the preparation method is simple in preparation process and strong in operability, and the obtained product is wide in practicability, low in mixing amount and the like, so that enterprises can occupy the market.
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Example 1:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 3.5 parts of aluminum hydroxide; 7 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 2:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 3.5 parts of aluminum hydroxide; 7 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 0.8 part of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 3:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 16 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1.2 parts of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 4:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 10 parts of aluminum hydroxide; 21 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1.5 parts of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 5:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 16 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1.8 parts of fluosilicate; NP-40.8 parts; 0.7 part of attapulgite; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, attapulgite, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and NP-4 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 6:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 16 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 0.2 part of fluosilicate; OP-100.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and OP-10 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 7:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
45 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 16 parts of hydrofluoric acid; 2.4 parts of magnesium oxide; 0.9 part of fluosilicate; OP-100.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and OP-10 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Example 8:
a high-strength alkali-free liquid accelerator comprises the following components in parts by weight:
37 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 23 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1 part of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; and 23 parts of water.
Preparation method of high-strength alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, reacting at the temperature of 90-95 ℃, obtaining a mixed solution after the reaction is finished, preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated, preserving the temperature for 1h, and finishing the fractionation of the free hydrofluoric acid in the mixed solution;
s2 preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to the proportion, putting the materials into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
Comparative example 1:
an alkali-free liquid accelerator has the same formula as that of example 2, and only has the difference that no fractional distillation is carried out in the preparation process of preparing the fluorine-aluminum complex solution from S1 in comparative example 1, namely, no heat preservation and heating stage is carried out after adding the hydrofluoric acid solution, and the synthesis of the alkali-free accelerator is directly carried out from S2.
The adhesive comprises the following components in parts by weight:
37 parts of aluminum sulfate; 3.5 parts of aluminum hydroxide; 7 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 0.8 part of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, and reacting at the temperature of 90-95 ℃ to obtain a mixed solution;
s2 preparation of alkali-free accelerator
Weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to a proportion, putting into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the alkali-free accelerator.
Comparative example 2:
an alkali-free liquid accelerator has the same formula as that of example 3, and only has the difference that no fractional distillation is carried out in the preparation process of preparing the fluorine-aluminum complex solution from S1 in comparative example 1, namely, no heat preservation and heating stage is carried out after adding the hydrofluoric acid solution, and the synthesis of the alkali-free accelerator is directly carried out from S2.
The adhesive comprises the following components in parts by weight:
37 parts of aluminum sulfate; 7 parts of aluminum hydroxide; 16 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1.2 parts of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, and reacting at the temperature of 90-95 ℃ to obtain a mixed solution;
s2 preparation of alkali-free accelerator
Weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to a proportion, putting into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the alkali-free accelerator.
Comparative example 3:
an alkali-free liquid accelerator has the same formula as that of example 4, and only has the difference that the preparation process of the aluminum fluoride complex solution prepared by S1 in comparative example 1 has no fractional distillation, namely, the heat preservation and heating stage is not needed after the hydrofluoric acid solution is added, and the synthesis of the alkali-free accelerator prepared by S2 is directly carried out.
The adhesive comprises the following components in parts by weight:
37 parts of aluminum sulfate; 10 parts of aluminum hydroxide; 21 parts of hydrofluoric acid; 8 parts of magnesium sulfate; 2.4 parts of magnesium oxide; 1.5 parts of fluosilicate; tween-200.8 parts; 0.7 part of precipitated hydrous magnesium silicate; 38 parts of water.
Preparation method of alkali-free liquid accelerator
S1 preparation of fluorine-aluminum complex solution
Weighing the following materials in proportion, firstly adding water, precipitated hydrous magnesium silicate, fluorosilicate and aluminum hydroxide, pre-dispersing for 0.5h, then continuously and slowly adding a hydrofluoric acid solution, and reacting at the temperature of 90-95 ℃ to obtain a mixed solution;
s2 preparation of alkali-free accelerator
Weighing the following materials, aluminum sulfate, magnesium sulfate and tween-20 according to a proportion, putting into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the alkali-free accelerator.
Description of the experiment:
when the alkali-free chlorine-free liquid accelerator provided by the formula and the process is used, the mixing amount is 4-6 wt% based on the weight of cement. The product of the invention is tested for the setting time of the net cement paste and the compressive strength of the cement mortar according to the requirements of Chinese building material industry standard & lt & gt accelerator for sprayed concrete & gt GB/T35159-2017. In the following examples, a Ruifeng cement P.O42.5 cement was used.
13 groups of examples 1 to 8, comparative examples 1 to 3, commercially available accelerators and blanks were subjected to experiments on setting time and compressive strength.
The test mixture ratio of the cement paste setting time is as follows: 400g of cement and 140g of water (containing water of the alkali-free liquid accelerator).
The test proportion of the compressive strength of the cement mortar is as follows: 900g of cement, 450g of water (containing water of the alkali-free liquid accelerator) and 1350g of standard sand.
And (3) testing the setting time, the 1d strength and the 28d strength ratio of the setting accelerator, and observing the states and the stability of the mother liquor and the setting accelerator. The specific technical indexes are shown in Table 1.
TABLE 1
All samples were good in stability after the product of the above example was left to stand at room temperature for 1 month; after standing at room temperature for 3 months, the examples 1, 2, 5, 6, and 7 and the comparative example 1 showed a delamination and a jelly-like phenomenon, and the other stability was good.
Comparative analysis according to Table 1, from the comparison of setting time, 1d compressive strength and 28d compressive strength specific properties:
transverse comparison:
in the aspect of condensation time: the setting time of the concrete accelerator can reach the standard requirement of accelerating agent for sprayed concrete under the condition of 5 percent of mixing amount of the examples 2-8 and the comparative examples 1-3, wherein the example 5 and the comparative example 3 perform the best performance;
1d, strength: according to the table 1, except that the comparative examples 1-3 are lower than 7Mpa, the other examples are all qualified, wherein the performances of the examples 1 and 2 are optimal;
③ 28 compression strength ratio: all examples are greater than 90%, with comparative examples 1-3 performing optimally.
Longitudinal comparison:
the examples 2 to 4 and comparative examples 1 to 3 were compared in terms of setting time, 1d compressive strength, 28d compressive strength ratio, and stability, and the examples were superior except for a slightly weak setting time.
In summary, the high-strength alkali-free liquid accelerator obtained in the embodiments 1 to 8 is obviously superior to the comparative examples 1 to 3 in the compressive strength of 1d, and it can be seen from the above table that the comprehensive performance of the embodiments 1 to 8 is higher than that of the comparative examples 1 to 3 and the accelerator sold on the market. At the same time, it can be further concluded from the above table that the overall performance of example 3 is optimal.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. A high-strength alkali-free liquid accelerator is characterized in that: the adhesive comprises the following components in parts by weight:
30-50 parts of aluminum sulfate; 3-8 parts of aluminum hydroxide; 5-25 parts of hydrofluoric acid; 0-20 parts of magnesium sulfate; 1.0-3.0 parts of magnesium oxide; 0.5-3 parts of fluorosilicate; 0.3-1.2 parts of an emulsifier; 0.2-1.0 part of a stabilizer; 30-50 parts of water;
the preparation method comprises the following steps:
s1: preparation of the Fluoroaluminum Complex solution
Weighing the following materials in proportion, adding water, a stabilizer, fluorosilicate and aluminum hydroxide, pre-dispersing, adding a hydrofluoric acid solution, obtaining a mixed solution after the reaction is finished, and preserving the temperature of the mixed solution at 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated;
s2: preparation of alkali-free accelerator
And after the fractionation is finished, stopping heat preservation, weighing the following materials, aluminum sulfate, magnesium sulfate and an emulsifier according to a proportion, putting the materials into the mixed solution, adding magnesium oxide after reacting for a certain time, continuing to react, and obtaining the high-strength alkali-free accelerator after the reaction is finished.
2. The high-strength alkali-free liquid accelerator according to claim 1, wherein: the adhesive comprises the following components in parts by weight:
35-45 parts of aluminum sulfate, 4-6 parts of aluminum hydroxide, 12-16 parts of hydrofluoric acid, 5-15 parts of magnesium sulfate, 1.5-2.5 parts of magnesium oxide and 0.5-2 parts of fluosilicate; 0.4-0.8 part of emulsifier, 0.5-0.7 part of stabilizer and 35-45 parts of water.
3. The high-strength alkali-free liquid accelerator according to claim 1, wherein: the fluosilicate is selected from magnesium fluosilicate or aluminum fluosilicate.
4. The high-strength alkali-free liquid accelerator according to claim 1, wherein: the emulsifier is selected from Tween-20, OP-10 or NP-4.
5. The high-strength alkali-free liquid accelerator according to claim 1, wherein: the stabilizer is precipitated hydrated magnesium silicate or attapulgite.
6. The high-strength alkali-free liquid accelerator according to claim 1, wherein:
in the step S1, in the preparation of the fluorine-aluminum complex solution, the materials are weighed according to the proportion, water, a stabilizer, fluosilicate and aluminum hydroxide are added firstly, after 0.5h of pre-dispersion, the hydrofluoric acid solution is continuously and slowly added, the reaction temperature is 90-95 ℃, a mixed solution is obtained after the reaction is finished, the mixed solution is insulated, and the insulation temperature is 85-90 ℃ until free hydrofluoric acid in the redundant mixed solution is fractionated.
7. The high-strength alkali-free liquid accelerator according to claim 1 or 6, wherein:
and S2, preparing the alkali-free accelerator, stopping heat preservation after fractionation, weighing the following materials according to a proportion, aluminum sulfate, magnesium sulfate and an emulsifier, putting the mixture into the mixed solution, reacting at the temperature of 60-65 ℃, adding magnesium oxide after stirring for 30min, supplementing water, continuing stirring for 1h, and cooling to room temperature after the reaction is finished to obtain the high-strength alkali-free accelerator.
8. Use of the high-strength alkali-free liquid accelerator according to claim 1 in shotcrete.
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| CN111646728B (en) * | 2020-07-01 | 2021-11-09 | 中建材中岩科技有限公司 | Quick-setting high-strength alkali-free liquid accelerator |
| CN111892322A (en) * | 2020-08-27 | 2020-11-06 | 衡阳市九州建材有限公司 | Concrete liquid accelerator |
| CN113024147B (en) * | 2021-03-24 | 2022-09-09 | 武汉源锦建材科技有限公司 | Alkali-free powdery accelerator for sprayed concrete and preparation method thereof |
| CN113121146B (en) * | 2021-04-16 | 2023-02-10 | 厦门路桥翔通建材科技有限公司 | Alkali-free accelerator and preparation method thereof |
| CN113264711A (en) * | 2021-06-28 | 2021-08-17 | 山西佳维新材料股份有限公司 | Powder alkali-free accelerator and preparation method, use method and application thereof |
| CN116161891A (en) * | 2021-11-25 | 2023-05-26 | 中国科学院过程工程研究所 | Sodium-free concrete accelerator and preparation method and application thereof |
| CN114772970B (en) * | 2022-05-11 | 2023-03-17 | 云南云天化股份有限公司 | Method for preparing liquid accelerator from wet-process aluminum fluoride production wastewater |
| CN115108750A (en) * | 2022-07-25 | 2022-09-27 | 云南云天化氟化学有限公司 | Alkali-free or low-alkali liquid accelerator and preparation method thereof |
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